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Catalytic conversion of lignocellulosic biomass to ne chemicals and fuels

Chun-Hui Zhou,*a Xi Xia,a Chun-Xiang Lin,b Dong-Shen Tonga and Jorge Beltraminib
Received 5th May 2011
DOI: 10.1039/c1cs15124j
Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for
sustainable production of chemicals and fuels. This critical review provides insights into the state-of
the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals
from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis,
solvolysis, liquefaction, pyrolysis, gasication, hydrogenolysis and hydrogenation are the major processes
presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and
various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast
pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasication is
typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are
the prime factors that aect the yield and composition of the target products. Most of processes yield a
complex mixture, leading to problematic upgrading and separation. An emerging technique is to
integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to
convert lignocellulosic biomass to value-added ne chemicals and bio-hydrocarbon fuels. And the
promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still
exist technological barriers that need to be overcome (229 references).
a

Research Group for Advanced Materials & Sustainable Catalysis

(AMSC), Breeding Base of State Key Laboratory of Green
Chemistry Synthesis Technology, College of Chemical Engineering
and Materials Science, Zhejiang University of Technology,
Hangzhou, 310032, China. E-mail: catalysis8@yahoo.com.cn,
chc.zhou@yahoo.com.cn
b
The School of Chemical Engineering, ARC Centre of Excellence for
Functional Nanomaterials, AIBN, The University of Queensland,
St. Lucia, QLD 4072, Australia

Dr Chun-Hui (Clayton) Zhou

is a Professor of Chemical
Engineering
and
Group
Leader of the Research Group
for
Advanced
Materials
and Sustainable Catalysis
(AMSC) at Zhejiang University of Technology as well as a
Member of the Editorial
Board of Applied Clay Science
(Elsevier). He worked as a
visiting Academic at the ARC
Center of Excellence for Functional Nanomaterials, AIBN,
the University of Queensland
Chun-Hui Zhou
in 20062007 and as Visiting
Professor at the Centre for Strategic Nano-fabrication, the
University of Western Australia in 2010. His research interests
include clay-based materials for miscellaneous applications,
sustainable catalysis for fuels and chemicals from biorenewable
resources, process intensication and advanced biomaterials.
5588

Chem. Soc. Rev., 2011, 40, 55885617

Introduction

The depletion of fossil fuel resources and the resulting adverse

eects on the global environment and climate are of major
academic, economic and political concern worldwide.13
As supplies of fossil fuels and related petrochemicals may soon
be limited, alternative solutions are sought. One alternative is to

Xi Xia has been a postgraduate under the supervision of

Prof. Chun-Hui Zhou in the
Research Group for Advanced
Materials
&
Sustainable
Catalysis, Zhejiang University
of Technology (ZJUT) since
September, 2008. He obtained
his Bachelors Degree in
Chemistry from Nanyang
Normal University in 2008
and his Masters degree of
Industrial Catalysis at ZJUT
in 2011. His research interests
are in advanced clay-based
Xi Xia
materials, catalysts and their
potential for the catalytic conversion of biomass into liquid fuels
and chemicals.

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The Royal Society of Chemistry 2011

develop a series of novel chemical processes based on renewable

feedstocks, typically biomass4 and biomass-derived chemicals.57
Biomass generally refers to organic materials such as wood,
grass, algae, agricultural crops and their residues and wastes,
including some animal waste.8 All of these materials originally
result from biological photosynthesis from readily available
atmospheric CO2, water and sunlight. Therefore, biomass is a
sustainable and green feedstock for the production of fuels and
ne chemicals with net zero carbon emission.
Biochemically, living systems produce a large number
of organic molecules such as carbohydrates, fats and oils,
phospholipids and glycolipids, waxes, steroids, proteins and
nucleotides. Among them, carbohydrates are the primary
energy-storage molecules. Carbohydrates are the main structural components of the cell walls of plants, in which the
carbohydrate polymers, namely cellulose and hemicellulose,
are tightly bound to the lignin.9 Any materials rich in cellulose,
hemicelluloses, and lignin are commonly referred to as lignocellulosic biomass.10 For example, wood, bamboo, grass and
their derived pulp and paper, and agricultural residues like
corn stover and sugarcane bagasse are typical sources of
lignocellulosic biomass.
Lignocellulosic biomass has received intensive attention
over the past decade. Many studies have shown that lignocellulosic biomass oers great potential to be used as a renewable
feedstock in abundance with easy availability.1114 Fig. 1 displays
the weight percentage of cellulose, hemicellulouse and lignin in
some typical biological sources such as pinaster,15 eucalyptus
globules,15 wheat straw,16 sorghum stalks,17 bamboo18 and
banana pseudo-stems.19 Generally, most of the lignocellulosic
biomass contains 3550% of cellulose, 2035% of hemi-cellulose,
and 1025% of lignin. Clearly, the major component of lignocellulosic biomass is cellulose. It is estimated that nearly half of
the organic carbon in the biosphere is present in the form of
cellulose. Therefore, in the context of processing lignocellulosic
biomass into fuels and valuable chemicals, the conversion of
cellulose is of paramount importance and worth being given
priority.1114
The development of the processes to convert lignocellulosic
biomass to fuels and value-added chemicals, however, remains
a big challenge. Firstly, the complex chemical composition of
lignocellulosic biomass makes it dicult to yield target fuels
and chemicals in a high yield and quality. Comparatively, as
to the three main components in lignocellulosic biomass,
the structure of cellulose is the simplest and most ordered.
Cellulose consists of only anhydrous glucose units, while
hemicelluloses contain many dierent sugar monomers. Consequently, cellulose is crystalline and hemicellulose just has a
random, amorphous structure. Dierent from carbohydratebased cellulose and hemicellulose, lignin is a class of complex,
cross-linked, three-dimensional biopolymers with phenylpropane units with relative hydrophobic and aromatic properties.
Those dierences in the chemical composition and structure in
lignin, hemicellulose and cellulose lead to their much dierent
reactivity. On one hand, for example, the decomposition of lignin
and hemicellulose is generally easier than that of cellulose.20,21
In other words, the decomposition and degradation of cellulose is
the most dicult and energy-consuming step in the conversion of
lignocellulosic biomass. As a result, to improving the reactivity of
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cellulose is a rst critical point. On the other hand, based on

their dierent reactivity, it is feasible to separate cellulose and
hemicellulose from lignin.22,23 Therefore, as reported in the
literature and discussed below, besides using the natural lignocellulosic biomass as the reactants, many researchers often choose
pure cellulose, in particular microcrystalline cellulose, as a model
of lignocellulosic biomass.
Over decades, many researchers have endeavored to explore
the production of fuels and chemicals from cellulose, which
is representative of lignocellulosic biomass.24,25 A cellulose
molecule has the generic chemical formula (C6H12O5)n.
It consists of a skeletal linear polysaccharide, in which glucosebased monomer units are jointed together through b-1,4-glycosidic linkages.26 The glucose units are further tightly bound by
extensive intramolecular and intermolecular hydrogen bonding
networks (Scheme 1a). The chain length of a cellulose molecule
ranges from about 100 to 14 000 units. Accordingly, cellulose has
an average molecular weight in the range of 3 00 0005 00 000.27
Noticeably, cellulose exists in the form of a robust crystalline
structure. And it is the principle scaolding component of all
plant cell walls. Such a cell wall polymer is neither soluble in water
nor easily digestible in the gastrointestinal tract of humans.
The changes in the types of chemical bonding and the
crystalline structure in polysaccharides, however, have signicant impacts on their physical properties and chemical
reactivity.23 For example, starch is also a polysaccharide with
the same general formula (C6H12O5)n as cellulose. Nevertheless, in each starch(amylose) molecule the neighboring glucose
units are linked through the 1,4 0 -a-glycosidic bond (Scheme 1b)
or the 1,6 0 -a-glycosidic bond (amylopectin), rather than the
1,4 0 -b-glycosidic bond in each cellulose molecule.28 This dierence has a profound eect on the three dimensional structure
and reactivity of the biopolymer molecule. Such 1,40 -a-glycosidic
linkages in starch are more easily attacked by acids or enzymes.
Thereby in the presence of acids or enzymes as catalysts starch is
more easily deconstructed into glucose monomers than cellulose.
For instance, starch is more easily fermented to yield ethanol
than cellulose. This is one of the major reasons that starches are
currently used as the starting materials for commercial bioethanol production, instead of cellulose.29,30 Nonetheless, any
large-scale processing of starch to fuels and chemicals readily
brings about strong competition between chemical production
and food demands.31 Therefore, in terms of both the abundance

Fig. 1 The weight percentage of cellulose, hemicelluloses and lignin in

some typical biological sources: pine pinaster,15 eucalyptus globules,15
wheat straw,16 sorghum stalks,17 bamboo18 and banana pseudo-stems.19

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Scheme 1 Comparison of the chemical structure of polysaccharides. (a) cellulose with 1,4 0 -b-glycosidic bonds and intra- and inter-chain hydrogen
bonding,27 Adapted and reprinted with permission from ref. 27. Copyright 2006 American Chemical Society; and (b) starch (amylose) with
1,4 0 -a-glycosidic bonds.28 Adapted and reprinted from ref. 28, Copyright 2003, with permission from Elsevier.

and availability from bioresources and little impact on food

supply, cellulosic materials as feedstocks are more practicable
and sustainable for the production of fuels and commodity
chemicals. In this context, the catalytic conversion of cellulose
to fuels and chemicals is more attractive and promising than that
of any other form of biomass like starch to bioethanol and
vegetable oil to biodiesel.3235
Still, lignocellulosic biomass such as wood, grass and agricultural residues are conventionally used as energy sources
typically by direct combustion.36 The principal utilization of
cellulose in industry is currently limited to textiles and paper
manufacturing.37 In some biological processes such as fermentation and enzymic catalysis, peculiar enzymes, bacteria and
other microorganisms are used to break down cellulose
molecules and thus a few commodity chemicals can be
obtained.38,39 Nevertheless, such biological processes generally
suer from unsolvable problems such as low eciencies,
narrow reaction conditions and limited scale of production.39,40 Chemocatalytic conversion of cellulose has been
around for some time, but it only receives serious attention
with the advent of a series of novel chemocatalytic reaction
routes since the fossil oil crisis in the 1970s.
However, besides the complexity of biological sources,
the inert chemical structure and the compositional ratio of
carbon, hydrogen and oxygen in molecules in lignocellulosic
biomass produce additional diculties in the chemocatalytic
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Chem. Soc. Rev., 2011, 40, 55885617

conversion of cellulose to valuable fuels and commodity

chemicals. In this context, the development of a new family
of highly active and selective catalyst systems is an essential
prerequisite for chemoselectively catalytic conversion of
lignocellulosic biomass to desired products.41 As such, this
article attempts to summarize and review recent advancements
in the dierent catalytic processes for the conversion of
lignocellulosic biomass, in particular cellulose, into potential
fuels and commodity chemicals.
Scheme 2 lists some typical ne chemicals and fuels which
can be produced by chemocatalytic conversion of cellulose
by dierent chemical processes. Clearly, a variety of fuels,
including ethanol, hydrogen, methane and chemicals such as
glucose, fructose, sorbitol, levulinic acid and lactic acid can be
obtained from catalytic conversion of lignocellulosic biomass.
Lignocellulosic biomass can also be used to produce syngas
(CO + H2) which can then be transformed into fuels and
myriad chemicals.
In many instances, depolymerization and hydrolysis of
cellulose to monomer glucose is regarded a necessary rst step.
Then glucose is further catalytically degraded into various
intermediates, chemicals and fuels (Scheme 2, Route A). Recent
research has paid much heed to accelerating the conversion
of lignocellulosic biomass in the presence of multifunctional
catalysts. The typical processes can be categorized as direct
liquefaction, gasication and aqueous-phase reforming,
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The Royal Society of Chemistry 2011

Scheme 2 Potential chemicals and fuels from the catalytic conversion of cellulose. (Route A: chemocatalytic conversion of cellulose into various
chemicals and fuels through glucose, Route B: Conversion of cellulose into various chemicals and fuels by a one-pass catalytic process in the
presence of a multifunctional catalyst).

pyrolysis. An emerging trend is to integrate catalytically thermochemical conversion with selectively catalytic hydrogenolysis
and hydrogenation with the addition of hydrogen.4244 Because
of the advantages of easy recovery and reusability of solid
catalysts, heterogeneous processes have been taking priority
over homogeneous catalytic processes. In addition, increasing
endeavors are being made to integrate the two- or multi-step
batch processes into a one-pass continuous conversion by using
well-designed multifunctional catalysts with an expectation to
transform lignocellulosic biomass into various commodity
chemicals in an ecient and environmentally friendly way
(Scheme 2, Route B).45

obtained. Interests in such acid-catalyzed hydrolysis have been

reignited because many ne and even platform chemicals can
be obtained from further conversion of reducing sugars.
Moreover, using a multistep fractionation process, various
ne chemicals and potential fuels can also be directly obtained
from acid processing of lignocellulosic biomass.46 Nevertheless, instead of the traditional use of liquid acids, nowadays
much attention is given to the use of solid catalysts such as
solid-supported Brnsted or Lewis acid reagent catalysts, acidmodied amorphous carbon, layered transition metal oxides,
and acidic resins for the depolymerization of lignocellulosic
biomass by hydrolysis (Tables 1 and 2).

2.1 Liquid acid-catalyzed hydrolysis

Catalytic hydrolysis of lignocellulosic biomass

Lignocellulosic biomass with cellulose as a main component is

generally resistant to hydrolysis in water. As such, the hydrolysis of cellulose in lignocellulosic biomass usually involves the
use of strong liquid acids as catalysts. Cellulose hydrolysis in
the presence of acids primarily yields reducing sugars, which
are a class of compounds that have an open chain with an
aldehyde or a ketone group. Typically, glucose and xylose are
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Acid-catalyzed hydrolysis of cellulose is a reaction in which

hydrogen cations (H+) and hydroxide anions (OH) from the
splitting of molecules of water react with polymeric cellulose
molecules, thereby yielding hydrolytic products by depolymerization. The discovery of such an acid-catalyzed reaction of
cellulose hydrolysis has a relatively long history.5577 Commercial microcrystalline cellulose is just a slightly depolymerized
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5591

Typical hydrolysis of lignocellulosic biomass or pure cellulose with H2O over liquid acid catalysts

Table 1
Catalyst

Feedstock

Reaction conditions

Typical products

Yield (%)

Researchers/Year

Ref.

H2SO4 (0.175 wt%)

Wood chips

Xylose

47.054.0

Emmel et al./2003

57

H2SO4 (0.05 wt%)

Filter paper

Reducing sugar

46.6

Zhuang et al./2006

53

H2SO4 (0.1 wt%)

Cotton

483 K, 2 min
B1.9 MPa
488 K, 35 min
4 MPa (H2O)
473 K, 6 min
0.1 MPa

144

Corn cobs

42.2
26.9
8.8
25.0

Kawamoto et al./2007

H2SO4 (0.5 wt%)

Levoglucosenone
Furfural
5-HMF
Xylose

Rivas et al./2008

55

Hu et al./2010

56

De Bari et al./2007

58

Liu et al./2006

59

H2SO4 (6.2 wt%)

Sugar maple
wood extract

SO2 impregnation

Aspen chips

HCl (5 wt%)

Walnut shells

HCl (20 wt%)/

+ [EMIM]Cl
CO2 + H2O
(100% saturation)
p-toluenesulfonic acid
+ C4MIMCl
H3PO4 (10 wt%)

Cellulose

Oxalic(0.1M) + NaCl

Cellulose

Cellulose
Cellulose
Potato peel

398 K, 165 min

368 K, 50 min
0.1MPa

478 K, 3 min
1.62 MPa (H2O)
523 K, 430 min
1.58.6 MPa (H2O)
378 K, 24 h

533 K, B2 min
2025 MPa CO2,
373 K, 5 h

408 K, 8 min

403 K, 6 h
3 MPa CO2

1

Xylose
Glucose
Rhamnose
Mannose
Galactose
Glucose
Xylose
Levulinic acid

161.6 g L
13.3 g L1
12.4 g L1
12.9 g L1
5.6 g L1
37.0 (wt%)
10.3 (wt%)
12.0

Glucose
HMF
Glucose

B90.0
57.0
B11.0

Binder et al./2010

68

Rogalinski et al./2008

64

Reducing sugar

35.0

Rinaldi et al./2008

90

Reducing sugar

82.5

Lenihan et al./2010

60

Glucose

2.83.9

Vom Stein et al./2010

67

5-HMF: 5-hydroxymethyl-2-furfural. Reducing sugar: mainly mono- and disaccharides with an aldehyde or a ketone group. [EMIM]Cl: 1-ethyl-3methylimidazolium chloride. C4MIMCl: 1-butyl-3-methylimidazolium chloride.

product of cellulose by liquid acid-catalyzed hydrolysis.47,48

More importantly, various products such as glucose, xylose,
arabinose and cellobiose and oligosaccharides can be readily
formed from liquid acid-catalyzed hydrolysis of cellulose
(Scheme 3).
Both inorganic liquid mineral acids such as H2SO4 and HCl,
and organic acids such as various carboxylic acids and
p-toluenesulfonic acid can be used as catalysts for the hydrolysis of cellulose. Various types of lignocellulosic biomass, for
example wood chips, sawdust, corn-cobs, and walnut shells,
have been tentatively processed by the liquid acid-catalyzed
hydrolysis (Table 1). However, it should be pointed out that
the hydrolysis mainly occurred in the cellulosic components in
these lignocellulosic sources with glucose and xylose as the
main products in most cases.
As summarized in Table 1, thus far H2SO4 has been the
most frequently used liquid acid catalyst in the hydrolysis of
lignocellulosic biomass. The reaction is usually conducted
at temperatures in the range of 363533 K and under atmospheric or higher pressure. In general, when a dilute acid
solution is used, higher temperature and longer reaction
time are necessary.49 In turn, when the hydrolysis reaction of
cellulose is conducted at low temperature and in a short
reaction time, concentrated acid is favorable. The treatment
of cellulose in a concentrated acid solution remarkably
accelerates such biopolymer molecules to be depolymerized
to monomers.50,51 Usually, the yield of reducing sugars
increases with increasing acid concentration. However, the
use of concentrated acid solutions could lead to a decrease of
the yield of glucose and xylose due to further degradation.
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Chem. Soc. Rev., 2011, 40, 55885617

Consequently, there is a substantial increase in the amount of

products of further degradation of glucose or xylose, for
example 5-hydroxymethyl-2-furfural (5-HMF).52 In addition,
taking into account the operation safety, equipment corrosion
and waste disposal, dilute acid is preferable for use in the
hydrolysis of cellulose.53 Furthermore, as for catalytic performances in the hydrolysis of lignocellulosic biomass with a high
content of hemicelluloses, dilute acid could be more eective
than concentrated acid.54
The deep insights into the eect of pressure on the conversion and distribution of products are scarcely reported.
However, it has been revealed that under atmospheric
pressure, catalytic hydrolysis of cellulose is also feasible with
both hydrolytic and dehydrated products.56 Clearly, under
atmospheric pressure, higher temperature, concentrated acid
and longer residence time are favorable to eectively depolymerize and degrade lignocellulosic biomass.
The impregnation of lignocellulosic biomass with acid
solution can lead to partial destruction of the cellulosic parts
in lignocellulosic biomass. Thereby such a pretreatment can
facilitate their further hydrolytic reaction. For example,
Emmel and co-workers57 reported that the pretreatment of
wood chips by impregnating them in 0.175 wt% H2SO4 led to
the remarkable hydrolysis of hemicellulose after the dilute
acid-catalyzed hydrolysis at 483 K for 2 min in steam. Thus
a yield of xylose up to 70% of its theoretical yield was
obtained in the water-soluble fraction. In this case, the pretreatment temperature was found to inuence the yield of
xylose. Interestingly, impregnation with gaseous SO2 proved
to be more eective than H2SO4 since a higher yield of
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Table 2

Typical hydrolysis of cellulose with H2O over solid acid catalysts

Catalyst

Feedstock

ACSO3H + COOH + OH

Cellulose

ACSO3H + COOH + OH

Cellulose

ACSO3H

Cellulose

ACSO3H (Sulfonation T = 523 K)

Cellulose

BCSO3H

Cellulose

HNbMoO6

Cellulose

H3PW12O40

Cellulose

H3PW12O40
CrCl3/LiCl + [C4MIM]Cl

Cellulose
+CH3OH
Cellulose

Naon/silica

Cellulose

Sulfonated silica/carbon
nanocomposites

Cellouse

Reaction conditions

Typical products

373 K, 3 h

373 K, 3 h

423 K, 24 h

Glucose
b-1,4-glucan
Glucose
b-1,4-glucan
Glucose

423 K, 24 h

MW (350 W),
373 K, 1 h
403 K, 12 h

453 K, 2 h

r473 K, 0.5 h
3 MPa
433 K,10 min

463 K, 24 h

423 K, 24 h

Yield (%)
a

Researchers/Year

Ref.

Suganuma et al./2008

82

Yamaguchi et al./2009

78

Onda et al./2008

79

Glucose

4.0
64.0
B8.1b
0.93
40.5
(C-%)
61.0

Pang et al./2010

83

Glucose

19.8

Wu et al./2010

81

Glucose

21.0

Takagaki et al./2008

88

Glucose
Levulinic acid
HMF
Methyl Glucosides

50.5
0.14
1.6
50.060.0

Tian et al./2010

86

Deng et al./2010

94

5-HMF

62.3

Wang et al./2011

89

Glucose
Levulinic acid
Glucose

9.0
2.0
50.0

Hegner et al./2010

76

Van de Vyver et al./2010

73

AC: Active carbon. BC: Biomass char. [C4MIM]Cl: 1-butyl-3-methylimidazolium chloride. MW: Microwave-assisted. a catalyst: 0.300 g; cellulose:
0.025 g; distilled water: 0.7 g. b catalyst: 0.300 g; cellulose: 0.25 g; distilled water: 2.25 g.

Scheme 3 Possible products from acid-catalyzed hydrolysis of cellulose.90 Adapted and reprinted with permission from ref. 90. Copyright 2008
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

glucose could be obtained.58 It was suggested that the addition

of SO2 catalyst (0.9% w/w dry raw material) reduced the
degree of polymerization of the cellulose by an average of
50%. In addition to the catalytic performances, another
noteworthy feature is that SO2 is less corrosive than the
H2SO4 solution.
In addition to reaction parameters such as temperature,
pressure, time and the concentration of acids, the type of acid
catalysts is also an inuential parameter for the distribution of
products in the catalytic hydrolysis of lignocellulosic biomass.
For example, in the presence of HCl acid in the hydrolysis
of walnut shells, the yield of levulinic acid could reach 12%.59
This result might indicate that HCl acid as a catalyst could
promote further catalytic dehydration of hydrolytic compounds,
thereby resulting in the remarkable generation of levulinic
acid. Dilute phosphoric acid is also an alternative catalyst.60
In a phosphate buer solution at pH 2, the hydrolysis and
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dissolution of Japanese red pine wood chips under subcritical

water conditions yielded hydrolytic saccharides and such further
dehydrated products as 5-HMF and furfural.61 It might indicate
that the presence of phosphate buer could play a pivotal role in
deep degradation of such a lignocellulosic biomass. However, in
the absence of a catalyst, water-soluble saccharides can also be
directly produced from the hydrolysis of lignocellulosic biomass,
for example sugi wood powder, in supercritical and subcritical
water.62
Despite the relatively high catalytic activity of H2SO4, HCl
and H3PO4 in the hydrolysis of cellulosic materials, by and large
their uses are still uneconomical because the process suers from
severe corrosion, costly separation and neutralization of waste
acids. These problems could be signicantly addressed provided
that carbonic acid (H2CO3), present in the form of a solution of
CO2 in water, can be used as a catalyst.63,64 First of all, carbonic
acid has little corrosive eect. Secondly, theoretically, it can be
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5593

easily removed by depressurization and thus it does not

leave any waste acid catalysts after reaction. Therefore, such a
carbonic acid-catalyzed process is environmentally friendly.
Rogalinski et al.64 reported that for the hydrolysis of cellulose
in subcritical water with pressurized CO2 at 533 K, the yield of
glucose could be signicantly increased by the acidication of
CO2 compared with that in pure water. Moreover, the onset of
the formation of glucose is shifted to a shorter residence time
due to the faster cleavage of 1,4 0 -b-glycosidic bonds facilitated
by carbonic acid. As for the catalytic mechanism, CO2 is
believed to promote the hydrolysis reaction of cellulose by the
formation and then dissociation of carbonic acid in water to give
active H+ cations, which then attack and break 1,40 -b-glycosidic
bonds in cellulose (eqn (1)).63,64
+
CO2 + H2O ! H2CO3 ! H+ + HCO
+ CO2
3 ! 2H
3
(1)

The avoidance of the use of strong liquid acids oers an

alternative approach to develop a green acid-catalyzed process. However, the insolubility of cellulose is another big
barrier that needs to be tackled. In this context, one possible
solution is to choose a suitable solvent. For instance, Recently
Lin et al.65 investigated the hydrolysis and degradation of
cotton cellulose treated with 1.39% HCl acid either in water or
in ethanol at 338 K for more than 1 h. A higher yield of
hydrolytic products was obtained in ethanol (2.445.04%)
than in water (1.121.50%). Moreover, the eect of the
reaction temperature on the yield of hydrolytic products in
ethanol was much greater than that in water. The phenomena
could be ascribed to the fact that the solubilization of cellulose
is enhanced by ethanol. This might well explain why cellulose
was more easily deconstructed in ethanol than in water.
The other alternative solution is to use a mixture of inorganic
and organic acids as catalysts.66 It has been found that
dicarboxylic acids, like oxalic and maleic acid, are able to
catalytically depolymerize cellulose, producing oligomers and
glucose.67 The third solution is to use ionic liquids as the
solvent and/or as the catalyst. Recently Binder and Raines68
reported a much eective process, in which water was gradually added to a catalytic system consisting of chloride ionic
liquid and acid catalysts (1-ethyl-3-methylimidazolium chloride,
[EMIM]Cl + H2SO4 or HCl). This method led to a nearly 90%
yield of glucose from cellulose and 7080% yield of sugars from
corn stover in a few hours. In comparison to other conventional
solvents and organic acids, however, the high cost of ionic
liquids and the problematic reusability might still hinder its
scale-up to commercial use.
Finally, in the liquid acid-catalyzed hydrolysis, besides acidic
catalysts, solvents and reaction variables, the source of lignocellulosic biomass is also an important factor. Obviously, the
molecular composition and arrangements of cellulose, hemicellulose and lignin in the plant cell wall changes throughout the
life of the plant. Moreover, they dier among plant species,
among tissues of a single species and even among geographical
regions of the plant. The dierences of chain length and
hydrogen bonding pattern between amorphous hemicellulose
and crystalline cellulose, for example, greatly aected the
distribution of glucose and oligomers in the liquid products
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Chem. Soc. Rev., 2011, 40, 55885617

after catalytic hydrolysis.69 In addition, even the size of biomass

feedstock particles may also be one of the important parameters.
These are also common points worth consideration in any other
processes discussed below.
2.2 Solid acid-catalyzed hydrolysis
Compared with homogeneous catalysts, heterogeneous solid
catalysts have several advantages. In particular, solid catalysts
can be easily separated from the liquid mixture after the
reaction, thereby allowing the possible reuse of catalysts,
along with the minimization of corrosion. Moreover, solid
acid catalysts have the potential to be easily applied to a
continuous ow xed-bed reactor. These merits have stimulated the research and development of recyclable solid acids as
replacements for the unrecyclable liquid acid catalysts in the
catalytic hydrolysis of lignocellulosic biomass.7072
As such, several types of solid acids, such as Naon,
Amberlyst, SO3H functionalized amorphous carbon or
mesoporous silica, H-form zeolites like HZSM-5, heteropolyacids and even metal oxides (for example, g-Al2O3) have
been explored on their catalytic performances in the catalytic
hydrolysis of lignocellulosic biomass. It has been shown that
solid Brnsted acid catalysts are indeed applicable for the
ecient hydrolysis of lignocellulosic biomass.74,75 Over solid
acid catalysts, the typical hydrolytic products like glucose
and xylose were also obtained, together with other chemicals
such as b-1,4-glucan, furfural, 5-HMF, and levulinic acid.
Furthermore, solid surface supported Lewis acid catalysts,
for example FeCl3 supported onto amorphous silica, can also
catalyze the hydrolysis of cellulose to glucose and then to
levulinic acid even under relatively mild conditions.76 However, in most cases, over solid catalysts the catalytic activity
and the selectivity to the desired products are quite low.
Therefore, a longer reaction time is needed to acquire the high
yield of glucose (Table 2), compared with liquid acid catalysts
(Table 1).
As shown in Scheme 4, a commonplace insight into the
hydrolysis reaction is that it involves the splitting of the
water molecule into hydrogen cations (H+) and hydroxide
anions (OH). In the presence of cellulose, the H+ attacks the
oxygen atom in the 1,4 0 -b-glycosidic linkage. Thus the 1,4 0 -bglycosidic linkage is broken to form a cyclic carbonium cation
with a chair shape. This step is considered as the ratedetermining step.77 Finally, glucose is formed by rapid ion
transfer of OH from the dissociation of water molecules to
the glucose unit-based carbonium cation. According to such a
reaction mechanism, that a solid acid catalyst and reaction
conditions favor the splitting of water will favor the hydrolysis
of cellulose. The splitting of a water molecule into hydrogen
cations (H+) and hydroxide anions (OH) can be regarded as
deprotonation. It was discovered that the catalytic activity of a
catalyst in the hydrolysis of cellulose increases with a decrease
in the deprotonation enthalpy (DPE) of water on the surface
of the solid acid catalyst.85 These ndings suggested that
stronger Brnsted acidity is more favorable to the catalytic
hydrolysis of cellulose. In addition, to some extent, an increase
in the amount of water had a positive eect on the breakage of
1,4 0 -b-glycosidic bonds and intramolecular hydrogen bonds in
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Scheme 4

Schematic mechanism of breakage of 1,4 0 -b-glycosidic bonds and formation of glucose in the hydrolysis of cellulose.

insoluble cellulose, thereby leading to more hydrolytic products.

Clearly, the formation of glucose requires more water than
the formation of b-1,4-glucan. Yamaguchi and co-workers78
revealed that the amount of water comparable to the solid
catalyst weight could lead to a maximum yield of glucose in
the heterogeneous catalytic hydrolysis reaction of cellulose.
On the one hand, the conditions conducive to splitting of
water molecules are needed. On the other hand, the conditions
should help to avoid deep degradation. Therefore, mildly
hydrothermal conditions were found favorable to the production of glucose from the hydrolysis of cellulose over solid acid
catalysts.78,79 Among a series of typical solid acid catalysts like
H-form zeolite, sulfated zirconia, sulfonated activated carbon
and Amberlyst polymer- based materials (Amberlyst, a commercially available sulfonated resin), as reported by Onda and
co-workers,79 sulfonated activated carbon showed a remarkably high yield of 40.5% of glucose (Fig. 2). Over such
sulfonated activated carbon catalysts, a selectivity of higher
than 90% to glucose was obtained. The catalysts could act in a
way similar to sulfonic acids containing the group SO3H,
which has fairly strong acidity. The remarkably catalytic
properties can be ascribed to the strong acidity of SO3H
functional groups and the hydrophobic planes on the surfaces
of such a catalyst, as well as its high hydrothermal stability.
Such systematic evaluation of a series of catalysts provided
valuable information and clues for the design and preparation
of a class of eective solid acid catalyst for catalytic hydrolysis
of cellulose by adjusting its surface acidity and hydrophilicity/
hydrophobicity.
It is worth noting that lignocellulosic biomass itself can be
made into carbon materials by carbonization.80 Bio-char or
activated carbon from lignocellulosic biomass such as bamboo,
wood, and coconut shells are well-documented catalyst supports. Microwave-assisted hydrolysis of cellulose in water over a
sulfonated bio-char acid catalyst (BC-SO3H) even showed a
much higher turnover number (TON, 1.331.73) compared to
that in dilute H2SO4 solution (TON, 0.02).81 The results were
likely due to the strong anity to 1,40 -b-glycosidic bonds of
cellulose on the surfaces of such catalysts, thereby accelerating
the activation of cellulose molecules. Microwave irradiation
could strengthen the collision of cellulose particles in the
reaction system. In addition, the surface of carbon solids can
be functionalized with several functional groups. For example,
Suganuma et al.82 described that a modied amorphous carbon
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Fig. 2 Catalytic hydrolysis of cellulose over various solid acid catalysts at 423 K. Reaction conditions: milled cellulose 45 mg, catalyst
50 mg, distilled water 5.0 mL, 24 h.79 Ref. 79Reproduced by
permission of the PCCP Owner Societies.

material can simultaneously bear SO3H, COOH, and OH

groups by means of partial carbonization of cellulose, followed
by sulfonation of the resulting amorphous carbon (Fig. 3).80
This strategy of catalyst preparation could eciently enhance
the performance of catalysts. Over such a catalyst, for example,
when the hydrolysis of microcrystalline cellulose was conducted
in a Pyrex reactor (catalyst = 0.300 g; cellulose = 0.025 g;
distilled water = 0.700 g) at 373 K for 3 h, the yield of glucose
and b-1,4-glucan reached 4% and 64%, respectively.82 The yield
of glucose was increased to 8.08% under the optimized conditions (catalyst = 0.300 g; cellulose = 0.25 g; distilled water =
2.25 g).78 The enhanced catalytic performance is attributed to
the good ability of such a material with a multi-functional
surface to adsorb b-1,4-glucan. This view might be partly
supported by the result that sulfonated silica/carbon nanocomposites exhibited high performance in the selective hydrolysis of cellulose into glucose.73 In this case, the hybrid surface
structure constituted interpenetrated silica and carbon components
which can greatly facilitate the adsorption of b-1,4-glucan on
the solid catalyst. More recently, it was suggested that elevating
the temperature of sulfonation during the preparation of
sulfonated carbon catalysts enhanced their catalytic properties
in the hydrolysis of cellulose.83 No matter what methods
were used, in essence, the presence of strong, accessible
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Fig. 3 Proposed schematic structure of the prepared carbon material

bearing SO3H, COOH, and OH functions.82 Reprinted with permission from ref. 82. Copyright 2008 American Chemical Society.

Brnsted acid sites on catalysts played a crucial role in the

catalytic hydrolysis of cellulose.
In addition to the surface-grafted or supported solid acids,
heteropolyacids such as tungstophosphoric acid H3PW12O408486
and HNbMoO687,88 can also be used as heterogeneous-like
catalysts for the catalytic hydrolysis of cellulose. For the hydrolysis of cellulose samples, H3PW12O40 and Sn0.75PW12O40
catalysts gave a higher yield of total reducing sugars than
H2SO4. A 50.5% yield of glucose with a selectivity higher than
90% were achieved over H3PW12O40 catalysts at 453 K for 2 h
with a mass ratio of 0.42 of cellulose to H3PW12O4086 Over a
series of catalysts like H3PW12O40, H4SiW12O40 and polyvalent
transition metal salts of PW12O403 (Ag+, Ca2+, Co2+, Y3+,
Sn4+, Sc3+, Ru3+, Fe3+, Hf4+, Ga3+ and Al3+), the highest
reaction rates were observed for the catalysts with moderate
Lewis acidity, such as Sn4+ and Ru3+-containing catalysts.86
In addition, layered transition metal oxides, for example
HNbMoO6, have also been found to be a class of eectively solid
acid catalyst for the hydrolysis of cellulosic materials to glucose.88
A 21% of the yield of glucose was obtained over layered
HNbMoO6 catalysts, even higher than that over Amberlyst-15
(3.4%) under the same reaction conditions (Table 2). The peculiar
layered structure might make facile the accessibility of saccharides
into the interlayer gallery of HNbMoO6, where the strong acidic
sites are located. Notably, such a layered structure exhibited good
properties of water tolerance, which is of particular importance in
a hydrolysis reaction.
Nevertheless, in the case of solid acid catalysts, there is a
signicantly poorer solidsolid reaction contact between
catalysts and lignocellulosic biomass as both lignocellulosic
biomass and solid cannot be dissolved in water. As such, either
the H+ ions from solid Brnsted acids or the active sites from
solid Lewis acid are dicult to access by reactants. Therefore,
the 1,4 0 -b-glycosidic bonds suer from diculty to be activated, attacked and then opened. Consequently, it results in a
low reaction activity. Moreover, in practice, there is another
diculty in the use of solid catalysts. To determine the true
conversion of lignocellulosic biomass remains an essential task
because it is not easy to separate unreacted cellulose from
sticky residues and various insoluble products that might
readily be adsorbed onto the solid acid catalysts.79 To tackle
these challenges, integrating the use of ionic liquids for
dissolving microcrystalline cellulose along with solid acids
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Chem. Soc. Rev., 2011, 40, 55885617

for catalytic splitting of cellulose into sugars may provide a

possible solution.89 For example, Rinaldi et al.90 showed
that the cellulose biopolymers were broken down into oligomers in the form of averaging ten glucose units catalyzed by
Amberlyst catalysts in 1-butyl-3-methylimidazolium chloride
(C4MIMCl) ionic liquid after 5 h. It was postulated that the
easy release of H+ ions into the solvent, the high surface area
and large pores in Amberlyst catalysts were probably crucial
factors to enable the long cellulose chains to be approached
and activated, thereby increasing the reactivity.
Furthermore, to further convert in situ hydrolytic glucose
to value-added commodity chemicals in a one-pot reaction
system is promising. So far the acidic solids have proved
to be eective in many reactions in organic synthesis. For
example, alkylation is also an acid-catalyzed reaction.91
After acidic resin Amberlyst catalyzed the hydrolysis of the
1,4 0 -b-glycosidic linkages in the cellulose polymeric chain to
give glucose, such acid catalysts could further catalyzed the
in situ alkylation of the hydroxyl groups at the C1 position of
the glucose as an intermediate. Consequently, cellulose
was directly converted into an environmentally friendly alkyl
glycoside surfactant in a one pot transformation.92 This stateof-the-art integration of consecutive reactions has also been
demonstrated in a recent work by Ignatyev et al.93 that
cellulose was fully converted into alkylglycosides under mild
conditions in the C4MIMCl ionic liquid in the presence of an
acidic catalyst. Primary alcohols like n-butanol and n-octanol
were used as alkylating reagents. In the reaction with n-butanol,
the yield of butylglucopyranoside isomers reached 86%. According to a well-established concept, the removal of intermediate
glucose by such alkylation can facilitate chemical equilibrium
to move forward, thereby leading to a higher conversion of
cellulose.

Catalytic solvolysis of lignocellulosic biomass

Apart from organic ionic liquid, certain organic reagents can

also physically and chemically modify cellulosic materials by
means of solvolysis, thereby promoting the contact between
cellulose molecules and surfaces of a solid acid catalyst. In this
context, the organic molecules act both as the solvents and as
the reactants. Consequently, they can signicantly facilitate
the catalytic conversion of lignocellulosic biomass over a solid
catalyst. Clearly, there is a chemical interaction between the
solvent and the solute lignocellulosic biomass. Therefore, the
inherent properties of solvents have a signicant eect on
products distribution. Moreover, it is also possible that
organic solvents react with intermediates, for example oligosaccharides or monomers, to yield secondary products. Deng
et al.94 reported that for the conversion of cellulose, the use
of methanol as a solvent led to the formation of methyl
glucosides in the presence of dilute H2SO4, heteropolyacids
or sulfonated solid acid catalysts under mild conditions
(r473 K). H3PW12O40 catalysts gave the highest TON
(B73 in 0.5 h) to methyl glucosides. Additionally, methyl
glucosides formed in methanol are more stable against
further degradation than glucose in water. Recently, it was
revealed that alcohol (methanol or ethanol) and water
showed a synergistic eect on direct liquefaction of biomass.95
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The 50 wt% co-solvent of either methanol-water or ethanolwater was found to be an eective mixed solvent for the
liquefaction of eastern white pine sawdust.
Comparatively, the dissolution of lignin and hemicellulose is
easier than that of cellulose owing to the abovementioned
dierences in their chemical structure. Therefore, the solvolysis and degradation of cellulose might be worth being
emphasized in the catalytic solvolysis of lignocellulosic biomass. Yamada et al.96 conducted the acid-catalyzed solvolysis
of cellulose using ethylene carbonate (EC) as an organic
reagent and 97% H2SO4 as catalyst. In comparison with
solvolysis by using polyethylene glycol (PEG), using EC as
a solvolysis reagent lead to a faster reaction rate. It was
suggested that cellulose with EC led rst to the formation of
glucosides, which then decomposed to form HMF derivatives
or levulinic acid as intermediates.96 In particular, HMF
derivatives could be either decomposed or polymerized to
form an insoluble fraction of products. Thereby, to obtain a
desired levulinic acid, how to control the formation of HMF
derivatives might be a critical issue. The solvolysis of lignocellulosic biomass can even proceed in the absence of catalyst
under hydrothermal conditions. The results showed that the
solvent such as acetone, ethylene glycol and toluene have a
profound eect on solvolytic product.97 In addition, solvolysis
can also be used to deal with intermediates from deploymerization or degradation of lignocellulosic biomass, for example
5-HMF, and levulinic acid.98 Thereby it might be applied to
acceleration of a catalytic solvolysis process mainly through
the solvolysis of intermediates.
Recently, Liu et al.99 investigated microwave-assisted organosolvolysis by a pretreatment of recalcitrant softwood in
aqueous glycerol with a series of organic and inorganic acids
with dierent pKa values including sulfuric, hydrochloric acid,
phosphoric, malonic, acetic, citric and lactic acids. It was
found that the eciency of pretreatment correlated linearly
with the pKa of the acids except malonic and phosphoric acids.
Noticeably, the organic acids, for example carboxylic acids,
could act simultaneously as the solvent, the reactant and the
catalyst. Moreover, organic acids can be possibly recovered
and reused by distillation or extraction. In addition to common organic acids like the carboxylic acids and sulfonic acids,
organic compounds bearing an OH or SH group might also
have certain acidity. Thus specic organic compounds can be
judiciously selected for both catalysis and solvolysis of lignocellulosic biomass. The method could provide an economical
alternative route to the selective conversion of cellulose to
small organic molecules.

4 Catalytically hydrothermal liquefaction of

lignocellulosic biomass
As discussed above, over certain acid catalysts, longer reaction
time, higher reaction temperature and pressure can readily
lead to deep degradation and decomposition of glucose,
xylose, arabinose and cellobiose and oligosaccharides which
are yielded from the hydrolysis of lignocellulosic biomass.
Thereby a liquid mixture product mainly consisting of
C2C6 organic compounds are obtained. In this respect, such
a process is usually called the liquefaction of lignocellulosic
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materials instead. Clearly, the objective of the liquefaction of

lignocellulosic materials is to produce low molecular-weight
liquid products, instead of glucose and xylose by hydrolysis.100
The catalytic liquefaction of lignocellulosic biomass is
generally performed in hydrothermal water similar to conditions
for hydrolysis at the temperature of 393653 K (Table 3).
An obvious advantage of the hydrothermal liquefaction process
is that it does not require the lignocellulosic biomass feedstock
to be pre-dried. Dierent from catalytic hydrolysis, however,
the liquefaction process of lignocellulosic biomass targets deep
degradation and decomposition of glucose through dehydration,
isomerization, decomposition and rearrangement, and so forth.101
The products are greatly changed when the type of catalyst is
substantially changed. For example, over halide catalysts, as
shown in Scheme 5, glucose, 5-HMF and furfural could respectively decompose to liquid products, such as levulinic acid,
5-HMF, furan and formic acid, in a parallel reaction.102 However,
over alkaline catalysts bio-oils and phenolic compounds are
dominantly produced (Table 3).
4.1 Hydrothermal liquefaction over halide and sulfate
catalysts
Recent literature reports that catalytic liquefaction of lignocellulosic biomass was often carried out over sulfate, halide
and oxide-based catalysts. Lewis acid catalysts could exhibit
good catalytic properties in hydrothermal liquefaction of
lignocellulosic biomass while catalytic hydrolysis is frequently
conducted in the presence of Brnsted acid catalysts (Table 3).
Several studies suggested, for example, that alkali and alkaline
earth metal chlorides were not eective in the conversion of
cellulose, while transition metal chlorides such as CrCl3,
FeCl3, CuCl2 and AlCl3,105,106 including a pair of these metal
chlorides (for example CuCl2 and CrCl2),107 exhibited high
catalytic activity. In particular, CrCl3 was found to be highly
active in the conversion of cellulose to levulinic acid, reaching
a yield of 67 mol% after 180 min at 473 K with a catalyst
dosage of 0.02 M and substrate concentration of 50 wt%.104 In
particular, the use of ionic liquids such as [C4MIM]Cl105,106
and [EMIM]Cl107 can eectively promote cellulose depolymerization, thereby quickening the hydrothermal liquefaction.
Recently, a one-step process for the conversion of lignocellulosic
biomass into valuable furanic compounds in ionic liquids
over CrCl3 under microwave irradiation was reported.105
The results showed that CrCl3 could eectively catalytically
convert lignocellulosic biomass into 5-HMF and furfural with
yields up to 52% and 31%, respectively, within a few minutes
without any pretreatment. It was postulated that CrCl3 in
[C4MIM]Cl might form complexes [C4MIM]n[CrCl3+n]. Thus,
in the presence of ionic liquid, the 1,4-glucosidic bonds were
weakened partially at the cellulose hydrolysis step under
microwave irradiation (400 W) because of coordination with
[CrCl3+n]n. As a result, it was more easily attacked by water
to form glucose and oligomers (Scheme 6).106 This coordination then promoted rapid mutarotation of the a-glucopyranose
anomer of glucose to the b- glucopyranose anomer of glucose
through hydrogen bonds of chloride anions with the hydroxyl
groups of glucose. The hemiacetal portion of b-glucopyranose
with [CrCl4] then formed a Cr3+ enolate anion complex and
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Catalytically hydrothermal liquefaction of lignocellulosic biomass or pure cellulose in an aqueous medium

Table 3
Catalyst

Feedstock

NiSO4 (400 ppm)

Cellulose

Reaction conditions Main products

573 K, 120 s
Lactic acid

Cellulose
523 K, 180 s (in N2) Glucose
LaCl3 (0.01 M)
5-HMF
Levulinic acid
Cellulose
423 K, 5 h
Acetic Acid
La/Al2O3 (0.34 wt%)

Malic Acid
Cellulose
573 K, 120 s
Lactic Acid
CoSO4 (400 ppm)

MW (400 W)
5-HMF
CrCl3 (3.6 wt%) + [C4MIM]Cl Cellulose
2 min, 0.1 MPa
Reducing sugar
Pine wood
MW (400 W)
5-HMF
CrCl36H2O+ [C4MIM]Cl
3 min, 0.1 MPa
Furfural
Cellulose
393 K, 8 min
5-HMF
CuCl2/CrCl2 + EMIM]Cl

Sorbitol
Cellulose
473 K, 3 h
Levulinic acid
CrCl3 (0.02 M)

Cellulose
608 K, 4.7 s
bio-oil
K2CO3 (0.5 wt%)
27.6 MPa
Empty palm
543 K, 20 min
Phenolic compounds
K2CO3 (1.0 M)
fruit bunch
2 MPa (H2O)
Corn stalk
647 K
bio-oil
Na2CO3 (1.0 wt%)
25 MPa (H2O)
Woody biomass
653 K, 1620 min
Heavy oil
Na2CO3
8 MPa (H2)
Sawdust
553 K, 15 min
Oil
Ca(OH)2 (0.0243 M)
KOH (0.5 M)
Walnut shells
523 K, 430 min,
Phenolic compounds
1.58.6 MPa
Lignin
573 K, 1 h
Phenolic compounds
Ba(OH)2 or Rb2CO3
2 MPa, H2
and oils
Ba(OH)2 or Rb2CO3
Sawdust/cornstalks 573 K, 1 h
Phenolic compounds
2 MPa, H2
and oils
Waste biomass
673 K, 10 min
Oil
K2CO3 + ZrO2
22.1 MPa

Yield (%)

Researchers/Year

Ref.

B6.6

Kong et al./2008

109

5.8 (wt%)
19.2 (wt%)
2.3 (wt%)
4.0 (wt%)
8.0 (wt%)
B9.5

Seri et al./2002

108

Schutt et al./2002

103

Kong et al./2008

109

Li et al./2009

106

Zhang et al./2010

105

Su et al./2010

107

Peng et al./2011

104

N/a

Kumar et al./2008

124

N/a

Akhtar et al./2008

119

47.2 (wt%)

Song et al./2004

123

53.3

Qian et al./2007

122

9.3 (wt%)
N/a

Karagoz et al./2004
Liu et al./2006

115
59

B53

Tymchyshyn et al./2010 126

62.0
20.0
52.0
31.0
57.5
1.27
67.0

B32 + 30/ Tymchyshyn et al./2010 126

32a + 25
913%
Hammerschmidt
125
et al. /2011
a

[EMIM]Cl: 1-ethyl-3-methylimidazolium chloride. [C4MIM]Cl: 1-n-butyl-3-methylimidazolium chloride. N/a: not available. MW: Microwave
irradiation. a data from reaction without catalysts, and the sum is the data with addition of catalysts.

it aroused the isomerization of glucose into fructose. Finally,

fructose is dehydrated to 5-HMF.106 Nonetheless, the heating
by microwave irradiation could also have an eect on cellulose
decomposition and 5-HMF formation. Though microwave
irradiation is facile at the laboratory scale, it might still be
dicult at large scale-up in industry. Furthermore, it cannot
be ignored that ionic liquids may also play a role in catalysis,
in addition to their role in facilitating the dissolution of
cellulose.107
Rare-earth metal salts or ions, for example lanthanum(III)
ions, which retain Lewis acid reactivity even in aqueous
solutions, have been used to catalyze the degradation of lignocellulosic biomass, typically cellulose.103 Earlier, Seri et al.108
showed that the conversion of cellulose degradation in water at
523 K in the presence of LaCl3 reached 80.3% after 180 s.
A 54.2 wt% yield of a water-soluble product mainly containing
5-HMF glucose and levulinic acid was obtained. In addition to
metal halides, sulfates can also be used as catalysts for the
catalytic liquefaction of cellulose. Furthermore, the reaction can
be directed towards a specic target product other than 5-HMF,
glucose and levulinic acid. Kong et al.109 revealed, for example,
that lactic acid can be produced from the catalytic hydrothermal
liquefaction of lignocellulosic biomass in the presence of dierent
transition metal ions like ZnSO4, NiSO4, CoSO4 or Cr2(SO4)3.
In comparison to a non-catalytic process, the addition of 400 ppm
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Chem. Soc. Rev., 2011, 40, 55885617

Ni2+ catalyst evidently increased the yield of lactic acid

from 3.25% to 6.62% at 573 K for 120 s in the hydrothermal
liquefaction microcrystalline cellulose samples in subcritical
water. It is noteworthy that lactic acid can also act as a platform
chemical from which lots of ne chemicals can be obtained.6
4.2 Hydrothermal liquefaction over alkaline catalysts
One of the important features of lignocellulosic biomass is that
it mainly contains two types of biopolymers, namely cellulosic
polymer and lignin polymer. Relatively speaking, the former
readily interacts with acid while the latter is apt to interact
with alkali. Therefore, in the presence of alkaline catalysts,
liquefaction of lignocellulosic biomass mainly leads to oil-like
products, although this process is usually conducted thermally
in an aqueous medium.110,111 In a sense, this process mimics
the conversion of ancient plant material into the crude oil.112
So far, various carbonates like Na2CO3, K2CO3, and hydroxides
such as KOH or Ca(OH)2 as catalysts have been evaluated
in the hydrothermal liquefaction for wood, agricultural
and civic wastes such as sugar cane bagasse and corn stalk
as sources of lignocellulosic biomass (Table 3). The so-called
bio-oil product is actually a complicated liquid mixture with a
wide range of compositions. It typically consists of glycoaldehyde dimers, 1,3-dihydroxyacetone dimers, anhydroglucose,
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Scheme 5 Main reaction pathways of degradation of major product, glucose, from cellulose hydrolysis over dierent catalysts.90,102 Adapted and
reprinted with permission from ref. 90. Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; Adapted and reprinted from ref. 102,
Copyright 2008, with permission from Elsevier.

Scheme 6 Direct conversion of cellulose to 5-HMF catalyzed with CrCl3 in [C4MIM]Cl (n = 13).106 [C4MIM]Cl: 1-n-butyl-3-methylimidazolium chloride. Reprinted from ref. 106, Copyright 2009, with permission from Elsevier.

soluble polyols, 5-HMF, furfural, organic acids, phenolic

compounds and even hydrocarbons. Therefore, an ecient
hydrothermal liquefaction process of lignocellulosic biomass
over alkaline catalysts oers remarkable potential for
simultaneously producing biofuels and value-added chemicals
by integrating it with proper separation and extraction
techniques.
Clearly, the reaction temperature and time and the type of
alkaline medium have a signicant eect on the reaction rate
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and product distribution.113,128 As for the eect of temperature on the reaction rate and the product distribution, for
example, earlier Minowa and co-workers114 showed that in the
presence of 0.826 wt% Na2CO3 under 3 MPa, the decomposition of cellulose started at a reaction temperature lower
than 453 K. Only water-soluble products were obtained at
temperatures below 533 K. The cellulose decomposed quickly
at 533573 K. Bio-oil was formed at temperatures above
533 K and its yield reached the highest values at 593613 K.
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5599

No cellulose remained after reaction at temperatures greater

than 573 K. Later, Karagoz and colleagues115 used a 0.0243 M
Ca(OH)2 solution as a solvent instead of pure water a in
liquefaction reaction of wood biomass. The results also
revealed that increasing the reaction temperature increased
the conversion of wood biomass and the total bio-oil yield.
Maximum bio-oil yield was found to be 8.5 wt% for a reaction
at 553 K for 15 min. Regarding these ndings, in general, an
obvious reason is that decomposition temperature for cellulose
and lignin is inherently dierent. Moreover, decomposition of
cellulose tends to yield polyols, alcohols and carboxylic acids
while decomposition of lignin principally leads to phenolic
compounds.
However, at elevated temperatures or over longer reaction
times, the occurrence of secondary reactions of bio-oil
products is increased so much that the yield of the bio-oil
decreases. In particular, for most of the lignocellulosic biomass treated at a temperature higher than 573 K a carbonization process tends to readily take place.116 The carbonization
could be eectively avoided at lower reaction temperature
in the presence of an appropriate catalyst. With regard to
low-temperature catalytic hydrothermal treatment of wood
biomass, several studies showed that the use of alkaline
catalysts increased the formation of the compounds such as
4-methyl-2-methoxy-phenol, 4-ethyl-2-methoxy-phenol and
benzenediol derivatives and decreased the solid residues, tar
and biochar.117,118 The role of catalysts in directing product
distribution is clearly proved by the observation that the furan
derivatives obtained from the thermal run were not observed
for the catalytic run. Moreover, the conversion and yield of
liquid products decreases in the following order: K2CO3 4
KOH 4 Na2CO3 4 NaOH.117119
It is most likely that the decomposition of lignocellulosic
biomass in water inhibits char formation. In particular, such a
process is conducted under subcritical or supercritical water
conditions. It is well-documented that near the critical point of
water (647 K, 22.1 MPa), the ionic concentration (Kw = [H+] 
[OH]; [H+] = [OH]) increases and water behaves as a
weakly polar solvent. Therefore, subcritical and supercritical
water conditions are often considered to be applied to the
liquefaction of lignocellulosic biomass. Earlier, Demirbas120
found that the yield of bio-oil from catalytic supercritical uid
extraction of oriental beech reached 68.6% at 573 K after
30 min in the presence of 20% wt NaOH. However, there are
also disadvantages in the use of subcritical or supercritical
water. Typically, the equipment corrosion by caustic hydroxides
is severely enhanced under subcritical and supercritical
water conditions. Therefore, in this aspect, alkali and alkaline
earth carbonate salts are favorable for use as catalysts. When
cellulose liquefaction is carried out in the presence of Na2CO3
under subcritical water and at a reaction temperature of 623 K,
bio-oil and gas were the main products, with little solid residue
formed.121 Qian et al.122 reported that when woody biomass
was liqueed at 653 K in the presence of Na2CO3 as a catalyst,
a yield of 53.3% of bio-oil, mainly composed of hydrocarbon,
aldehyde, ketone, hydroxybenzene and ester, was obtained.
However, Song et al.123 showed that in the case of isothermal
liquefaction of corn stalks in water without a catalyst, the
conversion was also very high, reaching 95.4 wt% with a liquid
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Chem. Soc. Rev., 2011, 40, 55885617

yield of 77.6% and gas production of 17.9%. When 1.0 wt%

Na2CO3 was added as a catalyst, the conversion rate remained
unchanged (95.7%), but the catalytic reaction favored the yield
of liquid products which increased to 88.0% and the gas
production decreased to 6.8%. Moreover, in the presence of a
catalyst, the bio-oil content in the liquid products sharply
increased from 33.4 wt% to 47.2 wt%. Clearly, not only does
the catalyst change the rate of the liquefaction reaction, but it
can also change the direction of the liquefaction reaction
towards dierent types of products.
The hydrothermal liquefaction is almost all conducted in a
batch reactor. However, it can be carried out in a continuous
ow reactor. For example, Kumar et al.124 revealed that when
using K2CO3 as a catalyst in a continuous ow reactor,
increasing the reaction temperature to the supercritical region,
or increasing the reaction time, hydrolytic oligomers and
monomers of cellulose samples were further degraded into
glycoaldehyde dimer, D-fructose, 1,3-dihydroxyacetone dimer,
anhydroglucose, 5-HMF, and furfural, thereby yielding biooils. To improve the selectivity to target compounds in the
bio-oil, Hammerschmidt and co-workers125 recently described
a continuous one-step process making use of two kinds of
catalysts, a homogeneous K2CO3 catalyst and a heterogeneous
ZrO2 catalyst. Such combination of a homogeneous system
with a heterogeneous system provides new ways to realize a
more ecient continuous process.
It should be noted that thermal liquefaction in an aqueous
solution might also undergo hydrolysis, pyrolysis and steam
gasication, in particular in super- or subcritical water. Such
complex reaction networks for cellulose decomposition in
homogeneous and heterogeneous reaction conditions under
subcritical water using Na2CO3, and Ni as catalysts and without catalysts, have been proposed by Fang and co-workers, as
shown in Scheme 7.121 In the course of the reaction, dissolved
compounds, for example part of cellulose, oligomers, glucose,
and levoglucosan and non-dissolved feedstock cellulose and
compounds, might undergo dierent reaction mechanisms,
thereby resulting in dierent intermediates and nal products.
At a high heating rate, a Na2CO3 catalyst resulted in more oil
while a Ni catalyst produced more gas. The dissolved reaction
paths in the homogenous phase were homogeneously hydrolyzed to glucose and other soluble pyrolytic products (e.g.
levoglucosan), which then further decomposed to acids, aldehydes, and alcohols of C1C3. Part of the glucose degraded to
furfurals and 5-HMF, which ultimately condensed to phenols
and dehydrated to levulinic and formic acids. The nondissolved reaction fraction in the heterogeneous phase possibly
underwent pyrolysis to yield a mixture of hydrocarbons,
aromatic derivatives and tar, randomly linked oligosaccharides,
light volatiles and gases via dehydration, cracking and ssion,
and rearrangement of the sugar units. Even for single cellulose as
a feedstock, the reaction mechanism is extraordinarily complicated. For lignocellulosic biomass, the presence of lignin and
hemicellulose certainly make it much more perplexing.
Among the components in bio-oils, phenolic compounds are
one type of typical, important product from the liquefaction
of lignocellulosic biomass after treatment with alkali. It is welldocumented that alkalis are exceptionally eective to extract and
convert lignin lignocellulosic biomass. Liu et al.59 showed that
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Scheme 7 Mechanism of cellulose decomposition promoted in homogeneous and heterogeneous environments in subcritical water. High heating
rates result in glucose char without catalyst, but more oil with Na2CO3 catalyst, and more gas with Ni catalyst.121 Reprinted with permission from
ref. 121. Copyright 2004 American Chemical Society.

the products from the hydrothermal conversion of walnut shells

catalyzed by 0.5 M KOH at 573 K were mainly phenol
derivatives, especially the methoxy phenolic compounds.
Clearly, these chemicals are readily derived from lignin. Owing
to the inherent multicomponent plant cells, small amounts
of cyclopentene derivatives and C1218 fatty acids were also
detected. Recently Tymchyshyn and colleagues126 described a
series of direct liquefaction of lignocellulosic wastes like sawdust
and cornstalks, and model biomass compounds like lignin and
cellulose in hot-compressed water at temperatures from 523 to
623 K in the presence of 2 MPa H2, with the addition of
Ba(OH)2 and Rb2CO3 catalysts. Signicant quantities of
phenolic compounds such as 2-methoxy-phenol, 4-ethyl-2methoxyphenol, and 2,6-dimethoxy-phenol were obtained from
the two lignocellulosic wastes and pure lignin. Yet the liquid
products from cellulose contained essentially carboxylic acids
and neutral compounds. Such experimental data evidently
revealed that lignin and cellulose inherently tend to result in
dierent categories of products. To bear this in mind is of much
importance in designing and developing a catalytic system for
hydrothermal liquefaction of lignocellulosic biomass to the
target products based on dierent goals.
As discussed above, catalytically hydrothermal liquefaction
of lignocellulosic biomass produces a very complex mixture of
liquid products along with some gases and solid residues and
tars. It makes the production of bio-oil from hydrothermal
liquefaction of lignocellulosic biomass very uneconomical at
present when compared to the costs of diesel or gasoline
production from fossil oils. Scheme 8 shows the separation
and extraction procedure proposed by Karagoz et al.117
It involves the complicated multistep extraction by several
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types of solvents. Moreover it needs inorganic acids for

neutralization and the separation of water-soluble organic
compounds in the water phase. Therefore, in addition to the
technical need for the improvement of the activity and selectivity
of catalysts, the novel technology for separation and extraction
of downstream products from hydrothermal liquefaction of
lignocellulosic biomass need to be developed.127,128 On the other
hand, such complexity in products is a reection of the complex
reaction mechanism in catalytic liquefaction of lignocellulosic
biomass. Thus far, researchers have not acquired in-depth
understanding of the reaction mechanism yet. To disclose it
certainly is conducive to developing such a process for the
commercial use. Finally, generally speaking, hydrothermal
liquefaction is relatively time-consuming and energy-intensive.
In this context, comparatively, fast pyrolysis, as discussed below,
is more promising.

Catalytic pyrolysis of lignocellulosic biomass

Pyrolysis of lignocellulosic biomass is generally a process of

thermal chemical decomposition in the absence of oxygen to
convert biomass into liquid products (bio-oils) together with
some gases and solid chars. Such a thermolysis process
simultaneously involves various reactions such as depolymerization,
dehydration,
decarboxylation,
esterication,
condensation, cyclization, and so forth.27,129,130 However,
dierent from catalytic liquefaction at lower temperature in
the aqueous phase, pyrolysis is usually conducted at temperatures greater than 773 K (Table 4). The liquid products are
commonly referred to as pyrolysis oils, which have been
identied as promising alternative renewable liquid fuels.131,132
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5.1 Fast pyrolysis mechanism

Scheme 8 Separation and extraction procedure.117 Reprinted with

permission from ref. 117, Copyright 2005, with permission from
Elsevier. WSH: Water soluble hydrocarbons (WSH and others in
wt% = 100  (oil1 + oil2 + oil3 + solid + gas). (Typical products
in oil 1: 2-Furancarboxaldehyd, 2-Methoxy-phenol, 4-Methyl-phenol,
4-Hydroxy-3-methoxy-benzeneacetic acid, 2-Hydroxy-3-methyl-2cyclopenten-1-one and Butylated hydroxytoluene; oil 2: 3-Methoxy-1propene, 4-oxo-Pentanoic acid, 5-Ethyldihydro-2(3H)-furanone;
oil 3: 2-Furancarboxaldehyde,2-Methoxy-phenol, 3-Methyl-phenol or
4-methyl-phenol, Eugenol, 4-Hydroxy-3-methoxy-benzeneaceticacidmethyl ester, 3-Acetyl-7,8-dimethoxy-2-methyl-1H-naptho[2,1-b]pyran-1one.

Similar to the liquid products from thermal liquefaction, the

pyrolysis oil is a complicated mixture of oxygenated and
deoxygenated compounds, typically consisting of organic
acids, aldehydes, ketones, esters, aromatic and phenolic derivatives, and even hydrocarbons. Accordingly, liquid pyrolysis
oils are normally acidic and emulsion-like uids containing
both aqueous phases and phenolic phases. Thus it is imperative to further upgrade pyrolysis oil so as to get useful liquid
hydrocarbon-like fuels and fuel additives.
Pyrolytic processing of lignocellulosic biomass can be
roughly classied into steam pyrolysis, fast pyrolysis in the
ow of an inert gas and vacuum pyrolysis. For all of these
approaches, a major, common objective is to improve the
selectivity of low molecular-weight substances with great
potential as fuels. As seen in Table 4, fast pyrolysis has been
the attractive subject of a lot of research over the past decade
because it is proven to be two to three times more economical
than liquefaction and gasication processes.133 Generally, four
parameters play a pivotal role in the catalytic activity and
selectivity of targeted pyrolysis oils. They are (1) the catalysts,
(2) heating rate of lignocellulosic biomass, (3) residence time of
reactants and the products inside the reactor, and (4) reaction
temperature.130 In addition, the atmosphere in the reactor is
inuential. For example, if the pyrolysis is conducted in the
presence of hydrogen, more hydrogenated products will be
obtained. Such an integrated pyrolysis with hydrogenation
process will be discussed in detail in Section 7.
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Chem. Soc. Rev., 2011, 40, 55885617

The fast pyrolysis reaction of lignocellulosic biomass undergoes a complex mechanism in oxygen-decient conditions at
high temperature, even though the reaction is conducted in an
inert atmosphere. Therefore, presently the investigation into
the mechanism could be simplied through the single use of
cellulose or lignin in a non-catalytic system. As shown in
Scheme 9, earlier Luo et al.137 proposed a fast pyrolysis
model of cellulose in an inert nitrogen atmosphere. Hydroxyacetaldehyde and 1-hydroxy-2-propanone was thought to
be produced from the decomposed fragments of activated
cellulose by competing against levoglucosan formation.
Meanwhile, the intermediate fragments might also decompose
to yield gases (COx). At low temperature, activated cellulose
would also directly decompose to produce char, CO2, and
H2O. A long residence time of intermediates like levoglucosan
in the reactor could lead to the secondary cracking reaction,
thereby leading to the formation of methanol, aldehyde, allyl
alcohol, glyoxal, furfural, 5-HMF and gases.
Regarding the gas products, a possible mechanism for fast
pyrolysis of cellulose in an inert gaseous atmosphere was
proposed by Lanza and co-workers recently,138 with the
following simplied decomposition sequence:
Cellulose - Gm, H2O

(2)

where Gm = short oligomers.

Gm, H2O - Cn, CO, H2O (+CO2, H2), with n r 4

(3)

Cn - CH4

(4)

CH4 + H2O - CO + 3H2

(5)

As depicted by the reaction paths in eqn (2)(5), cellulose

decomposes primarily to H2O and short oligomers (Gm),
which is then broken down to levoglucosan. The levoglucosan
easily breaks down to mainly form CO, H2O and hydrocarbons up to C4, along with minor CO2 and H2. In these
sequential reactions, butadiene was identied as a key intermediate. The hydrocarbons undergo further thermal cracking
reactions to yield CH4. The presence of H2O steam and
hydrocarbons results in a reforming reaction, nally leading
to chemical equilibrium composition among syngas and CH4.
According to this mechanism, H2 and CO can form in two
dierent reaction routes in eqn (2) and (5), respectively. And
the dierent pathways and rates in the formation of CO and
H2 explain why the ratio of CO to H2 is not constant under
dierent conditions, particularly at short residence time.
Therefore, it could be reasonably deduced that a longer
contact time is required if the aim is to produce syngas from
the fast pyrolysis of cellulose.
Although all of the abovementioned mechanisms have
proposed relatively simple reaction routes and identied key
intermediates in the non-catalyst system,137,138 it is evident
that fast pyrolysis involves a series of consecutive and parallel
reactions competing against each other among liquid products
and gaseous products. Nevertheless, as such reactions are
frequently conducted either in the gas or liquid phase in the
presence of homogenous and heterogeneous catalysts,139,140
the reaction mechanism might undergo far more complicated
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Table 4

Typical pyrolysis of lignocellulosic biomass in the presence or absence of catalysts

Feedstock

Catalyst

Reaction conditions

Typical products

Yield (%)

Researchers/Year

Ref.

Softwood bark and

Hardwood

No

Vacuum pyrolysis
773 K

N/a

Garcia-Perez et al./2007

134

Cellulose

No

135

No

20.045.9
12.5-27.4
60

Piskorz et al./2000

Soybean oil cake

Karagoz/2009

136

Cellulose

No

N/a

Lanza et al./2009

138

Cellulose

0.1wt% sulfuric or
polyphosphoric acid

144

Dobele et al./2005

142

Dobele et al./2005

142

Pine wood sawdust

Pretreated by 1wt%
phosphoric acid
Pretreated by 1%
phosphoric acid
NaOH

Chen et al./2008

146

Pine wood sawdust

Na2CO3

Fast pyrolysis, 773 K

Microwave heating

Chen et al./2008

146

Pine wood sawdust

Fe2(SO4)3

Fast pyrolysis, 773 K

Microwave heating

Chen et al./2008

146

Cellulose

ZSM-5

Carlson et al./2008

152

Pine sawdust

H-ZSM-5

Olazar et al./2000

150

Wood

Ni-ZSM-5

Fast Pyrolysis, 873 K,

240 s
Under He ow
Flash pyrolysis, 673773 K,
50 ms, under N2 ow
Fast pyrolysis, 873 K
Under He ow

42.2
26.9
8.8
33.6
14.1
25.2
29.8
53.3
0
2.08(area%)
45.28
1.03
2.58
0
50
0
31.1 (C%)

Kawamoto et al./2007

Wood

Flash pyrolysis
11231473 K, 3575 ms.
Pyrolysis, 773 K
Under N2 ow
Fast pyrolysis
1173 K, Z 3 h
Pyrolysis in tetramethylene
sulfone, 473 K, 6 min,
Under N2 ow
Fast pyrolysis, 773 K
Under He ow
Fast pyrolysis, 773 K
Under He ow
Fast pyrolysis, 773 K
Microwave heating

Parans, sterols
Fatty acid methyl
esters
Soluble solids
Liquid product
Liquid product

French et al./2009

151

Cellulose

CO, H2, CH4,

hydrocarbons
Levoglucosenone,
furfural
5-HMF
Levoglucosane
Levoglucosenone
Levoglucosane
Levoglucosenone
Acetol
Furfural
2-furanmethanol
Acetol
Furfural
2-furanmethanol
Acetol
Furfural
2-furanmethano
Aromatic
compounds
CO
C4-hydrocarbons
Hydrocarbons
Toluene

15.2 (C%)
15.9
16
3.5

n/a: no available. No. without catalyst.

Scheme 9 Modied model of fast pyrolysis of cellulose.137 Adapted and reprinted with permission from ref. 137. Copyright 2004 American
Chemical Society.

steps and reaction networks. Furthermore, many intermediate

products are more active than cellulose itself and polyols,
thereby making the reaction more perplexing. Such complex
reaction networks are still a puzzle and a barrier on the way to
understanding and utilizing cellulose by pyrolysis conversion
in a more ecient, economical way.
5.2

Catalytic fast pyrolysis

To increase the pyrolysis eciency and the content of the target

compounds in bio-oils, liquid acid such as H2SO4, hydrochloric
acid, phosphoric acid and Lewis acids can be used as a specic
pretreatment for pyrolysis of lignocellulosic biomass.141
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For example, Dobele et al.142 reported that the pretreatment

of pine wood sawdust and microcrystalline cellulose samples
with phosphoric acid or iron(III) sulfate drastically increased
the contents of levoglucosenone and levoglucosane in volatile
products obtained by a subsequent fast pyrolysis (Table 4).
These results were attributed to the catalysis of the cellulose
depolymerization and dehydration in the presence of acids
from the pretreatment. As for the use of iron ions, possibly
the cleavage of glycoside bonds were catalyzed by iron
oxihydroxide which formed during pretreatment of lignocellulosic biomass. As a result, such a pretreatment had a
positive eect on the yield of 1,6-anhydrosaccharides. With
regards to lignocellulosic biomass with a higher content of
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5603

lignin, higher concentration of phosphoric acid or iron(III)

sulfate was needed for pretreatment. Clearly, directly employing catalysts in the fast pyrolysis of lignocellulosic biomass can
remarkably improve the conversion and selectivity to targeted
products. As for the catalytic fast pyrolysis of microcrystalline
cellulose at 7731073 K by on-line analysis of the pyrolysis
vapors, Lu et al.143 revealed that SO42/SnO2 was the most
eective catalyst to yield 5-methyl furfural. The selectivity was
evidently changed with the change of catalyst support. For
example, the SO42/TiO2 catalyst favored the formation of
furfural, while SO42/ZrO2 favored the formation of furan.143
In addition, it is noteworthy that the type of solvent used
during the pyrolysis reaction also has a signicant impact on
the distribution of products. Kawamoto et al.144 depicted
the catalytic pyrolysis of cellulose catalyzed by H2SO4 in
tetramethylene sulfone (C4H8O2S) and found that the yield
of levoglucosenone, furfural, and 5-HMF reached up to 42.2%,
26.9%, and 8.8% (as mol% yield based on the glucose unit),
respectively, at 473 K for 6 min.144 Remarkably, the cellulose
pyrolysis in tetramethylene sulfone suered so little from carbonization reactions that the residues obtained from pyrolysis in
sulfolane were colorless. There, levoglucosan was identied as
the major anhydromonosaccharide formed during the pyrolysis
of cellulose.145 Tetramethylene sulfone is an aprotic polar solvent
and it could dissolve anhydromonosaccharides, therefore it could
prevent the polymerization and carbonization reaction. As such,
cellulose completely decomposed into soluble products in tetramethylene sulfone.145 In contrast, pyrolysis under nitrogen or in
dioctyl phthalate (a poor solvent for levoglucosan) produced
brown/black solid residues. The ndings indicated that the solvent
is also inuential in pyrolysis and it can be properly selected in
view of promoting dissolution of lignocellulosic biomass and/or
intermediates.
At present, the catalytic pyrolysis of lignocellulosic biomass
is often conducted in the presence of acid or alkaline catalysts
such as carbonates and hydroxides. Because the pyrolysis oils
yield various organic acids, the presence of alkaline species in
the reaction system has an important eect on the stability of
bio-oil. Phosphates, sulfates and chlorides also have certain
catalytic activity in the catalytic pyrolysis of lignocellulosic
biomass. With regard to the catalytic fast pyrolysis of pine
wood sawdust by microwave heating in a uidized reactor,
alkaline sodium compounds like NaOH, Na2CO3 and Na2SiO3
catalytically resulted in bio-oils rich in acetol, and to some
extent favored H2 formation while the use of the Fe2(SO4)3
catalyst favored the formation of fufural and 4-methyl-2methoxy-phenol.146 In addition, phosphates, sulfates and
chlorides could be used to replace corrosive alkaline catalysts
or corresponding acid catalysts. Other than catalysis, diammonium
phosphate (NH4)2HPO4 and diammonium sulfate (NH4)2SO4
could act as dehydrating agents upon heating during pyrolysis.
Therefore, at reaction temperatures of about 650750 K, a
pretreatment of water-extracted re wood by the impregnation
in about 1% of (NH4)2HPO4 or (NH4)2SO4 solution before
pyrolysis is able to increase the yields of levoglucosan,
5-methyl-2-furaldehyde and 2-acetylfuran in the range of
25%.147 Furthermore, alkali and alkaline earth metal
chlorides have also been investigated as catalysts. Shimada
and co-workers148 showed that the use of alkaline earth metal
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Chem. Soc. Rev., 2011, 40, 55885617

chlorides could substantially reduce the reaction temperature

from 673 to 423 K.
Recently, the catalytic pyrolysis of lignocellulosic biomass
over zeolites and supported solid catalysts have received
serious attention. In particular, it is attractive to employ
continuous fast pyrolysis of lignocellulosic biomass catalyzed
by solid catalysts which has obvious advantages over the use
of liquid acid catalysts in a batch reactor. More importantly,
the most desired product from the catalytic pyrolysis of
lignocellulosic biomass should be directed to hydrocarbonscontaining pyrolysis oils with high yield, similar to petrol
presently in use with easy storage and transportation. In
response, recent advances have shown that hydrocarbons
can indeed be produced in considerable quantities by fast
pyrolysis of biomass over zeolite and mesoporous catalysts
such as ZSM-5, Al-MCM-41.149 Such a catalytic fast pyrolysis
demonstrated an optimistic prospect for direct production of
high-octane pyrolysis oils from biomass for practical applications. For instance, Olazar et al.150 studied the fast pyrolysis of
pine sawdust with ZSM-5 in a spouted-bed reactor using
nitrogen as the carrier gas and observed a yield of aromatic
compounds of 12% (carbon). By using a semi-continuous ow
reactor with helium as carrier gas, French et al.151 revealed
that lignocellulosic biomass could be pyrolyzed at temperatures ranging from 673 to 873 K with a catalyst-to-biomass
ratio of 510 by weight over nickel, cobalt, iron, or galliumsubstituted ZSM-5, leading to an approximately 16 wt% yield
of hydrocarbons. Aromatic compounds like toluene151 and
even gasoline-like products152 can be obtained in remarkable
quantities even without using the hydrogen. However, over
solid catalysts at high temperature, the cracking and deoxygenating activity might decrease with time because of the coke
deposits formed on the solid catalyst.152 Finally, it should be
noted that the distribution of the pyrolysis products such as
charcoal, liquids and gaseous products are also strongly
inuenced by the physical and chemical characteristics of
the raw materials of lignocellulosic biomass. Therefore, the
cellulosic sources with adequate chemical composition should
be selected for the specic desired product, together with the
search for optimal reaction conditions and the catalysts. In this
context, the growth and productivity, ecological inuence and
cost of plant sources of lignocellulosic biomass should be taken
into consideration.

Catalytic gasication of lignocellulosic biomass

Gasication is usually referred to as a process of oxygendecient thermal decomposition of carbonaceous matter such
as coal, petroleum, biofuel, or lignocellulosic biomass with a
major objective to produce valuable gaseous products like
hydrogen or syngas.153155 In particular, the production of
hydrogen, an environmentally clean fuel, from cellulosic
biomass gasication is of much interest to scientists and
engineers. Through FischerTropsch synthesis techniques,
bio-syngas can also be converted into synthetic liquid fuels
and classied as clean and renewable transportation fuels.156
In this context, gasication plus FischerTropsch synthesis are
denoted as indirect liquefaction processes of ignocellulosic
biomass. Gasication of lignocellulosic biomass can also be
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performed at high temperatures with a controlled amount of

oxygen like catalytic partial oxidation.157 Provided that air is
used, the resultant products will contain nitrogen, thereby
leading to an additional problem of separation and purication. In many instances, gasication also produces small
amounts of tar, mainly composed of highly condensed polyaromatic hydrocarbons.158,159 To avoid such a problem and to
increase the eciency, biomass gasication in supercritical
water is of growing scientic and technical interest.160162 This
so-called steam gasication of cellulose, can be described by
the following reaction (eqn (6)).163165
0.59C6H12O6 + 0.7H2O - 1.42CH4 + 2.12CO2 + 1.4H2
(6)
Table 5 lists some typical reaction conditions and results in
catalytic gasication of lignocellulosic biomass in the presence
of steam. The possibly improved solubility of cellulosic materials in the supercritical water employed can greatly reduce
mass-transfer limitation. In addition, it can prevent catalyst
deactivation due to coke deposition by means of extracting the
coke precursor from the catalyst surface in the supercritical
water.166 Moreover, the use of supercritical water might
improve the hydrolysis and saccharization of cellulose in
extremely short residence times. Furthermore, Fushimi et al.
recently revealed that the evolutions of water-soluble tar and
gaseous products (CO, H2, CH4 and C2H4) are signicantly
suppressed by the interaction between cellulose and lignin.167
6.1

Gasication over supported noble metal catalysts

Supported Ru, Pt or Pd catalysts appear promising in

the catalytic gasication of lignocellulosic biomass under
supercritical conditions (Table 5). In addition, these catalysts
are commonly active for hydrogenation. Therefore, the H2
produced from gasication in turn might be a reactant for
in situ consecutive hydrogenation.
Various Ru-based catalysts such as RuO2, Ru/TiO2 and
Ru/C have been explored as catalysts in the catalytic gasication of lignocellulosic biomass. Earlier, Park et al.169 reported
the production of hydrogen from sewage disposals in supercritical water using RuO2 as the catalyst. The reaction was
more eective than conventional steam reforming to produce
hydrogen. Izumizaki and co-workers170 chose RuO2 as a
catalyst for the production of hydrogen from biomass in
supercritical water under argon atmosphere of 44 MPa at
723 K for 120 min. The amount of hydrogen in gaseous
mixtures was 15.0% from cellulose, 14.1% from pulp, 21.0%
from the mixture of cellulose and lignin, 16% from waste
paper and 27% from paper sludge, respectively. RuO2
evidently accelerated the thermal decomposition for cellulose
and pulp. However, for lignin, the catalytic performance could
be greatly suppressed because of the quick deactivation of the
RuO2 catalyst by coke and char formation.
A possible reaction model over such a RuO2 catalyst is
proposed as below.170

Org+ refers to an intermediate from the decomposed lignocellulosic biomass. According to such a proposition, CO was
formed through the cyclic oxidation-reduction reaction of
RuO2 with intermediate organics compounds (Org) and then
hydrogen was generated from the reduction of water by Ru2+
(eqn (7) and (8)). The hydrogen and CO could reacted to form
methane (eqn (9) and (10)).
CO + 3H2 - CH4 + H2O

(9)

2CO + 2H2 - CH4 + CO2

(10)

According to this reaction mechanism, a higher hydrogen ratio

in the product stream is subject to low methane formation. In
this case, the desired catalyst is the one which can signicantly
enhance the overall conversion of lignocellulosic biomass
whilst hindering reduced methane formation so that the yield
of hydrogen can be increased. Osada et al.171 showed that the
gasication of cellulose over Ru/TiO2 in supercritical water
conducted at 673 K for 15 min led to a high gas yield of
74.4 C% (calculation based on the carbon balance). Nevertheless, using the same reaction conditions without the presence of a catalyst, the gas yield and the water-soluble yield
were 11.3 C% and 39.0 C%, respectively. In this case, it is
reported that in the catalytic reaction no solid product was
formed.
In addition to the use of supercritical water conditions, to
tackle the insolubility of cellulosic materials in gasication,
there are a few reports suggesting that the derivative of
cellulose, carboxymethylcellulose (CMC) and acetyl cellulose,
can be mixed with particulate biomass and water to form a
uniform and stable viscous paste. Such a mixture can then be
gasied in a continuous ow system more eciently.172,173
Hao et al.173 found that the 10 wt% cellulose or sawdust
sample mixed with CMC (23 wt%) can be completely gasied
in supercritical water at 773 K, 27 MPa and for 20 min
residence time in the presence of a Ru/C catalyst. And the
experimental results suggested the catalytic activities in the
order as follows: Ru/C 4 Pd/C 4 nano-(CeZr)xO2 4 nanoCeO2 4 CeO2.
When acidic solid support, for example in a Pt/Al2O3
catalyst, was used, the catalytic gasication of lignocellulosic
biomass could consist of two main steps: (1) Al2O3 with
surface acidity could eectively act as a catalyst in the rst
step for the depolymerization of a lignocellulosic biomass
feedstock, similar to acid-catalyzed hydrolysis. As mentioned
previously, in supercritical water this depolymerization can
also occur to some extent even without catalysts. (2) The next
step is the gasication of water-soluble depolymerized products over Pt/Al2O3 in a catalytic reactor, producing H2, CO2,
and CH4 (eqn (11)).174,175 Similarly, in the case of Pt/C
catalyst in conversion of cellulose into hydrogen by aqueous
phase reforming process, it was proposed that this process
might involve slow hydrolysis of cellulose to glucose which
was catalyzed by the H+ reversibly formed in water during the
reaction and followed by rapid reforming of glucose to H2.176
H2 O

RuO2 + Org - Ru

2+

+ Org

+ 2CO

Ru2+ + 2H2O - RuO2 + 2H+ + H2

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(7)
(8)

3nH2 O

Cellulose ! C6 H12 O6 ! 6nC3n H2 O

11

Gasication of cellulose by the reforming reaction with H2O under

high temperature can be regarded as catalytic wet oxidation.103,177
Chem. Soc. Rev., 2011, 40, 55885617

5605

Some typical reaction conditions and results in catalytic gasication of cellulose or lignocellulosic biomass in the presence of steam

Table 5
Catalyst

Reactants

Reaction conditions

Typical products

Yield (%)

Researchers/Year

Ref.

Ru/TiO2 (2 wt%)

Cellulose + H2O

44.0
9.0
24.0 (wt%)

171

Sawdust + H2O

CH4
H2
H2

Osada et al./2004

Ru/C (5 wt%)

673 K, 15 min
1 MPa (argon gas)
773 K, 20 min
27 MPa (N2)
723 K, 2 h
44 MPa (argon gas)
623 K, 10 min
30 MPa (N2)
623 K, 3 h
30 MPa (N2)
1106 Ka, 60 ms
0.1 MPa (N2/O2 = 3.76)
623 K, 30 min or 1 h
18 MPa (N2)
973 K, in N2
10231063 K
Air-blown bubbling

Hao et al./2005

173

Izumizaki et al./2005

170

Usui et al./2000

178

Usui et al./2000

178

Dauenhauer et al./2007

188

Minowa et al./1999

192

Richardson et al./2010
Lahijani et al./2011

168
155

RuO2

Cellulose + H2O

Pt/Al2O3 (5 wt%)

Cellulose + H2O

Pd/Al2O3 (5 wt%)

Cellulose + H2O

Rh catalysts

Cellulose + H2O

Ni/SiO2Al2O3
(50 wt%)
Ni NP

Cellulose + H2O

Wood
Palm empty fruit
bunch

Temperature measured at 10 mm from the top of the catalytic bed.

Usui et al.178 studied how cellulose is gasied in hot-compressed

water at 623 K in the presence of a series of supported catalysts
(2 wt% loading) using Zr(OH)4, (CH3COCHQC(O)CH3)3Fe,
ferrocene, Ru3(CO)12, (CH3COCHQC(O)CH3)2Co, NiC2O4,
NiO, Ni(OH)2, 2NiCO33Ni(OH)2, PdI2, CuCO3Cu(OH)2,
(CH3CO2)2CuH2O,
(CH3COCHQC(O)CH3)2Cu,
and
Cu(OH)2. Among these catalysts, after reaction for 3 h,
5 wt% Pd supported on Al2O3 particularly showed the highest
catalytic activity, leading to a yield of H2 at 42.3 vol% and
CH4 at 7.7 vol%, respectively (Table 5). A possible two-step
mechanism is also proposed. Namely, rst the C2C10 unit
aldehydes, ketones, and organic acids were formed from
cellulose in hot compressed water and then these intermediates
were catalytically decomposed to give gaseous products mainly
consisting of H2, CH4, CO, and CO2. It is noteworthy that
using transition metal complexes as catalysts for the gasication of cellulose, oil and char were mainly produced with few
gaseous products.
Many studies have shown that the deactivation of a catalyst
in gasication of lignocellulosic biomass is often related to
the amount of coke deposition.179 In addition to catalyst
deactivation, the formation of tar readily causes trouble in
downstream equipment such as blocking and fouling. Therefore, a good catalyst should be multifunctional, including the
conducive roles in further catalytic steam reforming tar to
syngas and in the removal of the inactive biochar by catalytic
combustion. For example, Miyazawa et al.180 demonstrated
catalytic partial oxidation of tar over a multicomponent
Rh/CeO2/SiO2 catalyst for syngas production from lignocellulosic biomass. In addition, Asadullah and coworkers181
conducted a series of experiments on Rh-based catalysts
for gasication of cellulose and found that the Rh loading of
1.2  104 mol g1 catalyst supported on CeO2 exhibited
multiple functions during the gasication of microcrystalline
cellulose. The Rh/CeO2 catalysts remarkably increased the
conversion and inhibited the formation of methane, thereby
enhancing the yields of CO and H2, compared to Ru/CeO2,
Pd/CeO2, Ni/CeO2, Rh/Al2O3 and Rh/TiO2. These studies
suggested that Rh/CeO2 has great potential to be developed
as a catalyst for complete gasication of cellulose.
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Chem. Soc. Rev., 2011, 40, 55885617

CH4
H2
H2
CH4
H2
CH4
H2
CO
CO2 + H2 + CH4

32.1
13.7b
31.3
9.2 (vol%)
42.3
7.7 (vol%)
B52.0
B49.0
88.1

H2-rich gas
Gas

N/a
1.76 m3 gas kg1
biomass

L/per 100 g feedstock. NP: nanoparticles.

Finally, in addition to the catalysts and reaction variables,

the reactor also plays a role in gasication eciency and
product distribution.182186 Kaewluan et al.187 depicted a
bubbling uidized bed gasier having a high carbon conversion eciency (97.3%) and gasication eciency (80.2%) to
syngas from rubber wood chip. Dauenhauer and co-workers188
reported millisecond reforming, by which cellulose particles can
be converted extremely quickly into syngas on a hot Rh surface
without detectable deactivation from carbon formation.
6.2 Gasication over non-noble metal catalysts
It is well-documented that Ni, Fe, Co, and Cu-based catalysts
are eective for the water-gas shift reaction in which carbon
monoxide reacts with water to form CO2 and hydrogen
(eqn (12)).189 Therefore, when such kinds of solid catalysts
exist in the gasication of cellulose in the presence of steam,
the yield of hydrogen can be increased (eqn (13)), possibly
following a model involving in the watergas shift reaction
(eqn (12)).190
CO + H2O - CO2 + H2

(12)

decomposition

Cellulose ! water-soluble products

gasfication

! gasesH2 CO
Ni

13

methanation

! gasesCH4 CO2
Ni

However, the H2 is readily released from the liquid phase to

the gas phase. As a result, the catalyst cannot be in contact
with a large concentration of hydrogen. This might prevent the
methanation reaction from occurrence although methanation
is readily catalyzed by such types of catalysts (eqn (9) and
(10)). Recently, Sinag et al.191 compared the eect of nanosized and bulky ZnO and SnO2 on the water-gas shift reaction
in gasication of cellulose. The results showed that at 573 K
the watergas shift reaction proceeded faster over ZnO
catalysts than that over SnO2 catalysts. Therefore, a higher
yield of hydrogen was obtained in the presence of ZnO.
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The methanation reaction could be also suppressed under

subcritical and supercritical conditions. Minowa et al.192
reported that cellulose was gasied to hydrogen-rich gas over
a nickel catalyst supported on kieselguhr in hot-compressed
water at around 623 K and 18 MPa (subcritical conditions).
During gasication, the steam reforming reaction and methanation reaction both occurred. The gas phase equilibrium
composition was 4146 mol% CH4, 4749 mol% CO2 and
611 mol% H2. Recently, a series of catalysts such as nickel,
iron, copper, zinc, zirconium, ruthenium and RANEYs nickel
slurry were evaluated by Resende and Savage in the gasication of cellulose and lignin in supercritical water.193 The results
revealed that the metallic catalysts played a critical role in the
formation of gaseous product and the selectivity. The yield of
hydrogen gas could be increased to some degree over nickel or
copper by optimizing catalyst loading and the catalyst surface
area/biomass weight ratio. However, it is worth noting that, in
addition to the active component in a catalyst, usually the
acidity and basicity of a support is also an inuential factor
on product distribution and coke formation. Interestingly,
Tasaka and co-workers disclosed that steam reforming of tar
derived from cellulose gasication was eciently catalyzed
by 12 wt% Co/MgO catalyst at 873 K in a uidized bed
reactor. Over such a type of MgO supported catalysts, the
conversion of tar was found to increase with the amount of
Co loading.194,195 Those ndings indicate that the eciency
of gasication of lignocellulosic biomass could be greatly
enhanced by endowing the catalysts an additional function
of in situ removal of tar by catalytic steam reforming.

Integrated hydroprocessing

Because the dominant components in lignocellulosic biomass

are oxygen-rich cellulosic carbohydrates, the deploymerization
and degradation of lignocellulosic biomass by catalytic hydrolysis, solvolysis, liquefaction and pyrolysis primarily leads to
oxygenated molecules with carboxyl, keto, and/or hydroxyl
groups. Therefore, to yield targeted value-added chemicals
and liquid hydrocarbons as transportation fuels, most oxygenated molecules should be further deoxygenated along with
the formation of new CC bonds. In other words, an additional hydrogenation or hydroprocessing is needed.196 When
hydrogen is present in the reaction system over multifunctional catalysts, the partial or thorough removal of
oxygen from the oxygenated molecules and the formation
of CC bonds by hydrogenation and aldol condensation,
alkylation, or ketonization could occur simultaneously or
in situ consecutively.197 In addition, the catalytic hydrogenolysis of the glucosic carbonoxygen (CO and CQO) bonds in
cellulose and hemicelluloses and aromatic carbonoxygen
(CO) bonds in lignin may also take place in the presence
of hydrogen.198 Therefore, the technology of integrating
hydroprocessing with hydrolysis, solvolysis, liquefaction and
pyrolysis has increasingly received attention over the past decade.
And it has shown great potential for the production of the
commodity chemicals and fuels from lignocellulosic biomass.199
In the context of catalytic hydrogenation, supported metal
catalysts, for example Pt, Ru, Pd or Ni catalysts conventionally possess superior catalytic properties. Moreover, these
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supported metal catalysts have relatively large surface areas

with well-dispersed active metal sites. In addition, metalsupport interactions might signicantly contribute to the
activity, selectivity and stability of a catalyst. The introduction
of metal ions to a catalyst support can also modulate the
acidity/basicity on the surfaces, thereby possibly facilitating
the degradation of lignocellulosic biomass and reducing
carbon deposition by both the support and the active metal sites.
Over these supported catalytic metal catalysts, the eciency of
converting lignocellulosic biomass into hydrogenated products
can be greatly enhanced through complicated reaction networks
consisting of dehydration, dehydrogenation, hydrogenation,
isomerization, oligomerization, decarbonylation and decarboxylation, and so forth.
7.1 Integrated hydroprocessing to produce commodity
chemicals
As summarized in Table 6, presently many researchers use
cellulose as a model of lignocellulosic biomass for investigation
of the integrated hydroprocessing with hydrolysis to produce
commodity chemicals. A typical method is the combination of
supported Pt, Pd or Ru catalysts for hydrogenation with liquid
acid catalysts for hydrolysis. It oers a more ecient route to the
conversion of cellulose in a one-pot process reaction in the
aqueous phase to form C4 to C6 sugar alcohols, in particular
sorbitol, mannitol, and even ethylene glycol (Scheme 10, Table 6).
In particular, sorbitol can be transformed to fuels (hydrogen, light
alkanes and liquid alkanes) by aqueous-phase reforming or
to a number of high value-added chemicals by aqueous-phase
hydrodeoxygenation.200
The type of noble metal and support, the type of acid, acid
concentration and reaction time signicantly inuence cellulose conversion, carbon eciency and product distribution.201
Notably, the breakage of cellulose involves the cleavage of two
types of COC bonds: the 1,4-b-glycosidic bond connecting
two adjacent glucose monomers and the COC bond within
the glucose ring. Scheme 11 illustrates that over a ruthenium
nanocluster catalyst the cleavage of the 1,4 0 -b-glycosidic bond
at a dierent position will result in two dierent products:202
Cleavage at the C1O bond (position a) leads to dehydrated
sorbitol, while cleavage at the position b gives dehydroxyed
glucose. Therefore, to design a catalyst for a precise COC
cleavage is much conducive to the selectivity of the desired
product.
In addition, when noble metals are supported onto acidic
solids, possibly there is no need for the use of liquid acid. For
example, over Pt/g-Al2O3 catalysts, the surfaces of g-Al2O3
support have acidic sites, which can catalyze the hydrolysis of
cellulose to glucose, and then the CQO group in the glucose
molecule can be catalytically reduced by H2 over Pt species on
the surface of g-Al2O3, thereby leading to the formation
of hydrogenated products like sorbitol or mannitol.203,204
Nevertheless, g-Al2O3 itself is not acidic enough to eciently
hydrolyze cellulose.118 The additional acidity can be produced
from the interaction between Pt/Al2O3 and hydrogen.28 Under
the reaction conditions H2 may undergo heterolytic dissociative chemisorption of hydrogen on platinum atoms. Moreover,
hydrogen molecules activated on the platinum surface are able
Chem. Soc. Rev., 2011, 40, 55885617

5607

Integrated hydrolysis with hydroprocessing in the conversion of cellulose over supported catalysts

Table 6
Catalyst

Reactants

Reaction conditions

Main products

Yield (%)

Researchers/Year

Ref.

Ru/HUSY (2.5 wt%)

Cellulose + H2O + H2

Sorbitol

0.7

Fukuoka et al./2006

205

Ru/PVP (1 wt%)

Cellobiose + H2O + H2

23.18
1.4
39.3

202

Cellulose + H2O + H2

Sorbitol
Glucose
Hexitols

Yan et al./2006

Ru/C (4 wt%)

Luo et al./2007

206

Ru/C

Cellulose + H2O + H2

Geboers et al./2010

209

Cellulose + H2O + H2

Fukuoka et al./2006

205

Pt/PVPb (1 wt%)

Cellobiose + H2O + H2

Yan et al./2006

202

Pt/Al2O3 (2.5 wt%)

Cellulose + H2O + H2

Ji et al./2008

214

Pt/g-Al2O3

Cellulose + H2O + H2

Jolle et al./2009

204

HRuCl(CO)(PPh3)3, Rh/C

Cellulose + H2O + H2

Ignatyev et al./2010

208

2%Ni30%W2C/AC

Cellulose + H2O + H2

Ji et al./2008

214

Ni/carbon ber

Cellulose + H2O + H2

15%
14%
65
27
25
6
18.5
42.6
9.5
6.0
14.2
15
o1
26
74
3.9
1.9
61.0
50.0
6.2
12.8
2.5

211

Cellulose + H2O + H2

EG
1,2-PD
Polyol
Sorbitol
Sorbitol
Mannitol
Sorbitol
Glucose
Sorbitol
Mannitol
EG
Sorbitol
Glucose
Glucose
Sorbitol
Sorbitol
Mannitol
EG
Sorbitol
Mannitol
Erythritol
EG

Deng et al./2010

H4SiW12O40 and Ru/C

catalysts
Pt/g-Al2O3 (2.5 wt%)

463 K, 24 h
5 MPa (H2)
393 K, 12 h
4 MPa (H2)
518 K, 30 min
6 MPa (H2)
498 K, 5 min
6 MPa (H2) + CH3OH
463 K
5MPa (H2)
463 K, 24 h
5 MPa (H2)
393 K, 12 h
4 MPa (H2)
518 K, 30 min
6 MPa (H2)

de Vyver et al./2010

212

463 K, 24 h
5 MPa (H2)
423 K, 48 h
3.5 MPa (H2) + C4MIMCl
518 K, 30 min
6 MPa (H2)
463 K, 24 h
6 MPa (H2)

HUSY: H form of ultrastable Y zeolite. PVP: poly(Nvinyl-2-pyrrolidone). EG: ethylene glycol. PD: propanediol.

Scheme 10 Catalytic conversion of cellulose into polyols by integrated hydrolysis and hydrogenation.206,214 Adapted and reprinted with
permission from ref. 206. Copyright 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; Adapted and reprinted with permission from
ref. 214. Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

to exchange with protons of the hydroxy groups on the surface

of support Al2O3.203 These resultant H+ species can reversibly
spill over onto the surface of the catalyst support.203,204
Consequently, more Brnsted acid sites formed on the support
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Chem. Soc. Rev., 2011, 40, 55885617

which can then catalyze the hydrolysis of cellulose to glucose,

followed by metal-catalyzed hydrogenation. This is part of the
reasons that the presence of Pt/g-Al2O3 was found to signicantly increase the initial rate of dissolution-conversion as well
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Scheme 11 Cellulose structure and the potential monomers formed following cleavage of the COC bonds at positions a or b.202 Reprinted with
permission from ref. 202. Copyright 2006 American Chemical Society.

as the selectivity to polyols, especially sorbitol.203,204 Moreover, in most cases, the hydrolysis reaction could be a
rate-determining step.203207 Thus an ecient conversion of
cellulose into polyols can be realized through a combination of
hydrolysis and hydrogenation over such a class of bifunctional
supported metal catalysts.
In addition to Pt/g-Al2O3, on the surface of a carbonsupported Ru cluster (Ru/C) catalyst, H+ ions could also be
reversibly formed in situ in hot water, thereby resulting in both
catalytic hydrolysis and instantaneous hydrogenation.205,206
Moreover, integrated depolymerization of cellulose and
hydrogenation can be carried out using ionic liquid C4MIMCl
as a solvent in the presence of hydrogen.207 For example,
Ignatyev et al.208 recently discovered that the combination of a
heterogeneous metal catalyst and a homogeneous Ru catalyst
proved to be eective in such a process in the ionic liquid,
possibly because the Ru compound can enhance the transfer of
hydrogen to the metallic surface.
In addition, heteropoly acids together with supported noble
metal catalysts exhibit good performances in the conversion of
lignocellulosic biomass into valuable platform chemicals via
combined hydrolysis and hydrogenation.209 More recently,
Palkovits et al.210 showed that heteropoly acids together with
supported Ru catalysts show not only high activity but also
remarkable selectivity for sugar alcohols reaching up to 81%
yield of C4 to C6 sugar alcohols at 433 K for 7 h. Noticeably,
over supported Ru catalysts in the presence of basic solution,
an integrated one-pot conversion of cellulose could be developed to produce valuable specic polyols such as ethylene
glycol(EG), 1,2-propanediol, and 1,2,5-pentanetriol.211
Ni supported onto carbon is also an alternative catalyst
for a one-pot process of catalytic cellulose to polyols.212
Interestingly, a series of bimetallic catalysts including Ru-W/
AC, Ir-W/AC, Pd-W/AC, Pt-W/AC, Ni-W/SiC, and Ni-W/
TiO2 proved to be highly active and selective for the formation
of EG from cellulose.213 W was considered as a key component for degradation of cellulose, namely, the CC cracking
reactions, while the transition metals were mainly responsible
for the hydrogenation reactions of unsaturated intermediates.
Recently, Ji et al.214 demonstrated that supported tungsten
carbide catalysts can replace supported noble metal-based
catalysts to catalyze the degradation of cellulose. Moreover,
the use of Ni-W2C/AC catalysts showed remarkable selectivity towards EG with a yield up to 61 wt% after 30 min at
518 K and 6 MPa H2. In addition to integrated hydrolysis and
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hydrogenation, integrated aldol-condensation and hydrogenation of lignocellulosic biomass (corncobs) to produce

water-soluble C5C15 compounds was recently developed in
a single reactor system over Pd/WO3ZrO2 catalysts.215 The
promising progress means that there is still plenty of scope
to design more ecient catalysts for the one-pot catalytic
conversion of cellulose into value-added polyols and other
ne chemicals.
7.2 Integrated hydroprocessing to produce fuels
Another major objective of integrating hydroprocessing is to
convert lignocellulosic biomass to liquid hydrocarbons so that
they can directly replace the present gasoline or diesel fuels in
transportation applications. In this context, the processes of
hydrogenating hydrolytic compounds and hydrogenating
pyrolysis oil have been intensively investigated. Moreover,
lignocellulosic biomass is used more often as a starting
material, rather than pure cellulose model samples.
Studies have shown the possibilities for yielding diesel
and gasoline from lignocellulosic biomass by integrated
hydrogenation with acid-catalyzed hydrolysis. Recently it was
revealed, for example, that an integrated process can produce
gasoline with high octane numbers from maple wood.216
Such a process involves dilute acid-catalyzed (H2SO4, oxalic
acid) hydrolysis of maple wood into aqueous carbohydrate
solutions at 433 K, followed by aqueous phase hydrodeoxygenation of the resulting sugar solutions. Thus it led to
a product similar to gasoline with a carbon yield of up to 57%
and an estimated octane number of 96.5. Because of the complicated compositions of hydrolytic products, hydrogenation
deoxygenation of aqueous carbohydrate stream was realized
by a two-stage selectively catalytic process: rst the catalyst bed
contained a Ru/C catalyst at 393 K and the second catalyst
bed contained a Pt/zirconium phosphate catalyst at 518 K.
As discussed previously, pretreatment by organic solvent can
be signicantly helpful to dissolve or solvolyze lignin, cellulose
or hemicellulose in lignocellulosic biomass. Clearly, it is also
conducive to the integrated process of hydrolysis and hydrogenation. It was demonstrated that the pretreatment of cellulose in 1-hexanol at 623 K, followed by hydrocracking catalyzed
by Pt/HZSM-5(23) at 673 K in the presence of hydrogen,
produced C2C9 alkanes with a remarkable yield up to 89%.217
Compounds other than hydrocarbons from lignocellulosic
materials also have potential for use as fuels. For example,
Lange and co-workers218 reported that over bifunctional
Chem. Soc. Rev., 2011, 40, 55885617

5609

catalysts Pt/TiO2 and Pt/ZSM-5 valeric esters as biofuels were

produced from lignocellulosic materials. The synthesis of
valeric biofuels consisted of acid hydrolysis of lignocellulosic
materials to levulinic acid, hydrogenation of the levulinic
acid to g-valerolactone (gVL) and valeric acid (VA), and its
subsequent esterication to valeric biofuels (Scheme 12A).
According to the proposed mechanism for the conversion of
gVL to VA over bifunctional catalysts (Scheme 12B), the
optimal production of VA requires a balancing of the acidic
and hydrogenation functionalities of the bifunctional metal/
zeolite catalyst. Therefore, changing the ratio of metal to
zeolite led to dierent intermediates and products. Low metal
loading onto zeolite resulted in an increase in the coproduction
of pentenoic acid. High metal loading favored the formation
of methyl tetrahydrofuran (MTHF), pentanal/pentanol,
and/or pentane/butane. In particular, it is noteworthy that
valeric biofuels were found to be fully compatible for blending
with gasoline or diesel. More recently, Serrano-Ruiz et al.
described219,220 that the deconstruction of cellulose in an
aqueous solution of H2SO4 yielded an equimolar mixture of
levulinic acid and formic acid. The formic acid could then be
decomposed into H2 and CO2 and thus H2 was consumed
to reduce levulinic acid to GVL in the H2SO4 solution over a
Ru/C catalyst. Moreover, the formation of GVL brought
about easy separation and recycling of the used H2SO4 in
the cellulose deconstruction reactor. Remarkably, in a single
reactor by means of a dual catalyst bed of Pd/Nb2O5 and
ceria-zirconia; levulinic acid and GVL could be catalytically
upgraded to 5-nonanone and then liquid hydrocarbon fuels
similar to diesel and gasoline.
In addition to hydrotreating hydrolytic products, hydroprocessing of the pyrolysis oil of lignocellulosic biomass is also
a promising option for the production of CH-rich fuels from
lignocellulosic biomass. One example is the extraordinary nding by Vispute and co-workers documenting that the further
hydroprocessing of the pyrolysis oil greatly increased its intrinsic
hydrogen content, thereby leading to light olens and aromatic
hydrocarbons.221 Over zeolite catalyst, the yield of aromatic
hydrocarbons and light olens could be tuned through the
amount of hydrogen added to the biomass feedstock during
hydroprocessing. As discussed, fast pyrolysis of lignocellulosic
biomass is a relatively economical way to produce pyrolysis
oil. As such, an ecient integrated hydrotreating denitely
oers remarkable potential for production of renewable liquid
bio-based diesel and gasoline from lignocellulosic biomass.

Prospects and concluding remarks

The limitation in the availability and sustainability of fossil

fuels such as coal, petroleum and natural gas, along with the
negative ecological and environmental impacts of their uses
compel many researchers to develop new environmentally
friendly processes on the basis of renewable feedstocks.222
Lignocellulosic biomass, in particular plant cell wall-based
cellulose, is the most abundant and bio-renewable resource
on earth. It has been considered as one of the most attractive
alternatives to replace fossil resources for the production of
fuels, fuel additives and ne chemicals.
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Chem. Soc. Rev., 2011, 40, 55885617

Over the past decades, several catalytic systems, namely

hydrolysis, liquefaction, gasication, pyrolysis and deoxygenation/hydrogenation for the catalytic conversion of lignocellulosic biomass have increasingly received attention.
Generally, acid catalysts are primarily used in the catalytic
hydrolysis of lignocellulosic biomass to produce glucose and
xylose; metal supported catalysts and zeolites are primarily
evaluated in the gasication of lignocellulosic biomass to
produce H2 or syngas; and alkaline catalysts are dominantly
investigated in the fast pyrolysis. Over multifunctional
catalysts, the integrated hydroprocessing of lignocellulosic
biomass specically lead to sorbitol and mannitol, EG or
hydrocarbon-based diesel and gasoline.
Theoretically, the scale-up of a chemocatalytic process of
lignocellulosic biomass can produce fuels and chemicals in
large quantities in a short reaction period. However, no matter
what type of catalytic processes employed, present techniques
have not yet met the required level for commercialization in an
economical and environmentally stable fashion. The present
liquefaction, gasication and pyrolysis of lignocellulosic
biomass yield very complicated products in most cases. The
upgrading and separation of products requires high energy
consumption. The invention of a heterogeneously solid
catalyst with extraordinary activity and selectivity remains
an essential task of paramount importance. A paradoxical,
challenging issue is that the heterogeneous reaction over solid
catalysts commonly suers from low catalytic activity due to
the solidsolid contact between the insoluble lignocellulosic
biomass and solid catalyst. The utilization of ionic liquids as
solvents and/or as catalysts provides an alternative solution.
However, the use of the ionic liquids might bring about new
problems such as separation and extraction of the targeted
products and increased cost.
Fast pyrolysis of lignocellulosic biomass has proven to be
more ecient than liquefaction and gasication. It is expected
that upgraded pyrolysis oils can act as fuels directly. However,
provided that gasication processes can selectively produce
syngas with cost-eective cleaning technology, it is also
certainly of great commercial value because syngas can be
converted to clean fuels and ne chemicals by currently
available catalytic technologies, for example syngas to methanol
and ethanol and then to hydrocarbons and olens.223 Also, it
is much desired to directly gasify and pyrolyze wet lignocellulosic biomass because drying lignocellulosic biomass is an
energy-intensive and time-consuming operation.224
In the short term, fossil crude oils are still available in large
quantities. Therefore, the overall costs for production of
commodity fuels and chemicals from lignocellulosic biomass
processes by the present catalytic techniques are indeed
less competitive in comparison with large-scales petroleum
industries. In the long run, integrated production of fuels
and ne commodity chemicals from lignocellulosic biomass
feedstocks could be the most economical and renewable alternative in a sustainable society. To put the catalytic processes
of lignocellulosic biomass into use, some key points to be
addressed in the years ahead include:
(1) In-depth understanding of the mechanism of the heterogeneously catalytic conversion of lignocellulosic biomass. It is
necessary to identify the specic features of each component
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Scheme 12 (A) Reaction scheme and key performance factors for the individual process steps in the formation of valeric biofuels (S: selectivity,
[mol%]; P: productivity, [tproductm3reactorh1]; and C: concentration, [wt%]). LA: levulinic acid; gVL: g-valerolactone; VA: valeric acid; EV: ethyl
valerate; EG: ethylene glycol; PG: propylene glycol; IER: acidic ion-exchange resin. (B) Probable reaction mechanism for the conversion of gVL to
VA over bifunctional catalysts. MTHF: methyl tetrahydrofuran; Pe: 1-pentanol; PV: Pentyl valerate; PeOH: 1-pentanol.218 Adapted and reprinted
with permission from ref. 218. Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

such as cellulose, lignocelluloses and lignin in the reaction

networks. It includes the interrelationship among the feedstock, the catalyst, the reaction conditions and the product
distribution. In addition, the specic sources of lignocellulosic
biomass to the desired products should also be established
more clearly in each process.225 In-depth insights into the
structure of cellulose and lignin biopolymers from the interdisciplinary sciences of plant and chemistry are surely useful to
develop a strategy to convert it.226,227
(2) Strategic design and preparation of multifunctional catalysts for highly active and selective conversion of lignocellulosic
biomass. This involves acidity, basicity, metal-support interactions, the shape of catalyst particles, mechanical and chemical
stability, deactivation and reusability. Because of the peculiar
features of lignocellulosic biomass and its degraded products,
novel reactors and separation systems, including process intensication, for continuous one-pass or one-pot operation should be
developed so as to reduce the cost, minimize waste disposal and
energy consumption, and maximize the productivity.
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The Royal Society of Chemistry 2011

(3) Ecient production of liquid hydrocarbons from lignocellulosic biomass. Firstly, because liquid hydrocarbons can be
directly used in current engines, there is no need for building new
infrastructure for distribution. Secondly, if lignocellulosic biomass
is to replace fossil oils mostly or even completely, similar to
current petroleum industry, the large-scale process of lignocellulosic biomass should, for the most part, produce hydrocarbon-based liquid fuels. In addition to platform chemicals
and ne chemicals, the identication of certain specic chemicals
in the conversion of lignocellulosic biomass as a new type of fuels
or fuel additives is also of much signicance.228,229
All in all, to make the catalytic conversion of lignocellulosic
biomass into valuable products practicable is one of the most
important topics in chemistry. It involves many challenges and
opportunities. Though the studies on the chemocatalytic conversion of cellulose have received intensive attention over the
past few decades and many breakthroughs have been achieved
therein. A noteworthy thing is that besides cellulose, lignocellulosic biomass contains hemicellulose and lignin which are
Chem. Soc. Rev., 2011, 40, 55885617

5611

still less investigated. Moreover, the most workable and

economical way could be to use lignocellulosic biomass
directly, rather than pure cellulose. It might be right to say
that the technology of catalytic conversion of lignocellulosic
biomass to fuels and chemicals remains in its infancy. Recent
advances have shown an exciting prospect of putting catalytic
conversion of lignocellulosic biomass to good use. The next
decades will certainly witness the use and growth of catalytic
production of fuels and chemicals from lignocellulosic
biomass with continual technological innovations.

Acknowledgements
We thank anonymous reviewers for thoroughly reading the
manuscript, providing thoughtful, valuable suggestions and
comments on the early version of this manuscript, which
almost lead to a new version. We would like to thank the
Publishers for granting permissions to reproduce copyright
materials cited or adapted in this manuscript. The results and
illustrations are credited to the original researchers to whom
we would like to express our gratitude. The authors wish to
acknowledge the nancial support from the Distinguished
Young Scholar Grants from the Natural Scientic Foundation
of Zhejiang Province (R4100436), the National Natural
Scientic Foundation of China (20773110, 20541002), Zhejiang
151 talents project, and Project (2009C14G2020021) from
Science and Technology Department of Zhejiang Provincial
Government for the related research and development. The
authors wish to acknowledge the support of the School
of Chemical Engineering and ARC Centre of Excellence
for Functional Nanomaterials, AIBN in the University of
Queensland during the preparation of this work.

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